Infrared Spectroscopy –Analytical chemistry laboratory, ICT Prague

THEORY

An important tool of the analytic and organic chemists is Infrared (IR) Spectroscopy. IR
spectra are acquired on a special instrument, called an IR spectrometer. IR is used to gather
information about compound's structure, assess its purity, and sometimes to identify it.

Infrared radiation is that part of the electromagnetic spectrum between the visible and
microwave regions. Infrared radiation is absorbed by organic molecules and converted into
energy of molecular vibration, either stretching (bond enlargement and contraction) or
bending (change in angle between three atoms). Different types of bonds, and thus different
functional groups, absorb infrared radiation of different wavelengths. An IR spectrum is a plot
of wavenumber, cm-1, (X-axis) vs percent transmittance or absorbance (Y-axis).

The Electromagnetic Spectrum

Infrared refers to that part of the electromagnetic spectrum between the visible and microwave
regions. Electromagnetic spectrum refers to the seemingly diverse collection of radiant
energy, from cosmic rays to X-rays to visible light to microwaves, each of which can be
considered as a wave or particle traveling at the speed of light. These waves differ from each
other in the length and frequency, as illustrated in Figure 1.

Figure 1. The electromagnetic spectrum.

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1

2
 A = -log T

Note how the same spectrum appears when plotted as T and when plotted as A (Figure 2).

Figure 2. The IR spectrum of octane, plotted as transmission (left) and absorbance (right).

As illustrated in the spectrum of octane, even simple organic molecules give rise to complex
IR spectra. Both the complexity and the wavenumbers of the peaks in the spectra give the
chemist information about the molecule. The complexity is useful to match an experimental
spectrum with that of a known compound with a peak-by peak correlation.

The wavenumbers (sometimes referred to as frequencies) at which an organic molecule

absorbs radiation give information on functional groups present in the molecule. Certain
groups of atoms absorb energy and therefore, give rise to bands at approximately the same
frequencies. The chemist analyzes a spectrum with the help of tables which correlate
frequencies with functional groups. The theory behind this relationship is discussed in the
next section on molecular vibrations.

Molecular vibrations

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 3.

3:

Figure 4 : Stretching (bond enlargement and contraction) and bending (change in angle
between three atoms) vibrational modes for CO2.

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 5

Figure 5 : Stretching and bending vibrational modes for a CH2 group.

Stretching Vibrations

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Figure 6 : Energy curve for a vibrating spring (left) and energy constrained to
quantum mechanical model (right).

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 7.

f is the force constant of the bond

Figure 7: Energy curve for an anharmonic oscillator (showing the vibrational levels for a
vibrating bond).

Equation 7 shows the relationship of bond strength and atomic mass to the wavenumber at
which a molecule will absorb IR radiation. As the force constant increases, the vibrational
frequency (wavenumber) also increases. As the mass of the atoms increases, the vibration
frequency decreases.

IR spectra of liquids can be most often measured either in the cell composed of two windows
(drop of the sample is placed between two plates of NaCl or KBr forming a thin film) or using
the Attenuated Total Reflectance (ATR) technique.

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Attenuated Total Reflectance Technique

Internal reflection spectrometry or attenuated total reflectance infrared (ATR/IR)

spectrometry can provide valuable information related to the chemical structure of molecules
studied. Mid-infrared spectra are obtained by putting the liquid sample against an internal
reflection element (IRE), e.g., zinc selenide (ZnSe) or germanium (Ge). IR radiation is
focused onto the end of the IRE. Light enters the IRE and reflects down the length of the
crystal. At each internal reflection, the IR radiation actually penetrates a short distance (few
micrometers) from the surface of the IRE into the liquid sample. It is this unique physical
phenomenon that enables one to obtain infrared spectra of samples placed in contact with the
IRE.

Sample

ATR technique: Total internal reflection at the interface of an internal

reflection element. Depth of penetration of the evanescent wave is
approximately few micrometers.

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EXPERIMENTAL TASKS

A. IR spectra analysis of organic compounds

1. Measure the IR spectrum of polystyrene.

2. Identify the bands characteristic for aromatic and aliphatic moieties (–CH2- ) in the
spectrum of polystyrene.
3. Measure the spectra of two liquid organic samples, both in the cell (transmission
measurement) and also using Attenuated Total Reflectance (ATR) technique.
4. Assign the peaks to characteristic vibrations and resolve whether the samples contain
aromatic or aliphatic ( –CH2- and –CH3) moieties, or both together. If there are other
characteristic groups in the samples, specify them (-OH, –NH2, –NO2, double bond,
carbonyles C=O, -CN, etc.)

B. IR spectra analysis of inorganic compounds

5. Measure the IR spectrum of H2O by ATR technique.

6. Measure the IR spectrum of an inorganic sample dissolved in H2O.
7. Transfer both the spectra from transmittance unit to absorbance.
8. Subtract the spectrum of H2O from spectrum of the sample.
9. Identify the bands characteristic for the inorganic compound.
10. Compare the spectrum with the spectra of standards in a database and resolve what
anion the sample contains.

How to work?

A.

ad 2) Use the table of characteristic vibrations to specify what bands in the polystyrene
spectrum come from aromatic and what from –CH2- parts. Before you print the spectrum out,
use Analyze/Find Peaks to ascribe wavenumbers to the particular peaks.

ad 3) Measure the spectra of both the samples in a liquid cell as well as by the ATR
technique. You shoud get finally four spectra, two for each sample. Firstly, measure the
background of the spectrometer using “Collect Background“ mode (with empty sample
compartment in case of the transmission measurement or with a clean and dry IRE crystal in
case of ATR). Start accumulation of 32 and 64 scans for transmission and ATR technique,
respectively. Then insert the sample and start its measurement using “Collect Sample“ mode.
Similarly as for the backgroud, accumulate the same number of scans for the sample. After
the measurement of the sample is done, save the spectrum on the hard-drive (C:\My
Documents\Spectra Avatar X). Assign the wavenumbers to particular bands using
Analyze/Find Peaks and print the spectra out, each sample (two spectra, one from the cell and
second one from ATR) on one sheet, using “Stack Spectra“.

ad 4) Use the table of characteristic vibrations to specify characteristic groups seen in the
spectra.

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B.

ad 5) The spectrum of H2O has been generally measured by teacher.

ad 6) Firstly, measure the background of a spectrometer using “Collect Background“ mode

(with a clean and dry ATR crystal, 64 scans). Then insert the sample and start its
measurement using “Collect Sample“ mode. After the measurement is done, save the
spectrum on the hard-drive (C:\My Documents\Spectra Avatar X). Clean the ATR crystal by
H2O.

ad 7) Open both the spectra, H2O and sample, in a one spectral window. Use
Process/Absorbance to transfer them from transmittance unit to absorbance.

ad 8) Subtract the spectrum of H2O from the spectrum of sample using Process/Subtract.

ad 9) Identify the bands characteristic for the inorganic compound and assign wavenumbers
to the particular bands using Analyze/Find Peaks.

ad 10) Compare the spectrum of the sample with the spectra of standards in a database
(C:\My Documents\Spectra Avatar 1\Anorganika) and resolve what anion the sample
contains. Print out the spectra of sample and appropriate standard in a range of 1700 - 800
cm-1.

Finally, prepare laboratory report. It should involve:

 Title of the task

 Your name, date, group number
 Short introduction (3-4 sentences). Say about principle of IR spectroscopy and for
what purpose this technique can be used
 Spectrum of polystyrene and its interpretation summarized in a table
 Spectra of both the organic samples and their interpretation summarized in two tables
 Spectrum of inorganic sample comapred to the spectrum from the database
 Conclusion. What functional groups did you find in each sample

Questions to be answered:
1. Explain the principle of IR spectroscopy.
2. Explain how the ATR technique works.
3. What is a relationship between wavelength and wavenumber?
4. What is a unit usually used for wavenumber?
5. What is a relationship between absorbance and transmittance?
6. How many degrees of freedom nonliner and liner molecules have?
7. Explain the difference between stretching and bending vibrations.
8. Formulate Hook`s low – explain symbols.

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APPENDIX

How to analyze IR spectra?

If you have followed this tutorial group-by-group, you will realize that in even rather simple,
mono-functional molecules there are so many IR bands that it is not feasible to assign every
band in an IR spectrum. Instead, look for tell-tale bands - the region from 4000-1300 cm-1 is
particularly useful for determining the presence of specific functional groups. Look at the
distinctive bands of the common functional bands:

3500-3300 cm-1 N–H stretch amines

3500-3200 cm-1 O–H stretch alcohols, a broad, strong band
3100-3000 cm-1 C–H stretch alkenes, aromates
3000-2850 cm-1 C–H stretch alkanes
1750-1670 cm-1 C=O stretch ketones, aldehydes, esters
1680-1640 cm-1 C=C stretch alkenes

Begin by looking in the region from 4000-1300 cm-1. Look at the C–H stretching bands
around 3000 cm-1:

Indicates:
alkyl groups (present in most organic
Are any or all to the right of 3000 cm-1?
molecules)
Are any or all to the left of 3000 cm-1? a C=C bond or aromatic group in the molecule

Look for a carbonyl in the region 1750-1670 cm-1. If there is such a band:

Indicates:
Is an O–H band also present? a carboxylic acid group
Is a C–O band also present? an ester
Is an aldehydic C–H band also present? an aldehyde
Is an N–H band also present? an amide
Are none of the above present? a ketone

(also check the exact position of the carbonyl band for clues as to the type of
carbonyl compound it is:

 1705-1710 cm-1 for carboxylic acid group

 1710 cm-1 for ketone
 1720-1725 cm-1 for aldehyde
 1735-1745 cm-1 for ester
 1680-1700 cm-1 for carbonyl conected to aromatic group

Look for a broad O–H band in the region 3500-3200 cm-1. If there is such a band:

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 Indicates:
Is an O–H band present? an alcohol or phenol

Look for a single or double sharp N–H band in the region 3400-3250 cm-1. If there is such a
band:

Indicates:
Are there two bands? a primary amine
Is there only one band? a secondary amine

Other structural features to check for:

Indicates:
an ether (or an ester if there is a carbonyl band
Are there C–O stretches?
too)
Is there a C=C stretching band? an alkene
Are there aromatic stretching bands? an aromatic
Is there a C≡C band? an alkyne
Are there -NO2 bands? a nitro compound

If there is an absence of major functional group bands in the region 4000-1300 cm-1 (other
than –CH2- and –CH3), the compound is probably a strict hydrocarbon.

Also check the region from 900-650 cm-1. Aromatics, alkyl halides, carboxylic acids, amines,
and amides show moderate or strong absorption bands (bending vibrations) in this region.

As a beginning student, you should not try to assign or interpret every peak in the spectrum.
Concentrate on learning the major bands and recognizing their presence and absence in any
given spectrum.

Table of Characteristic IR Absorptions

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frequency, cm–1 bond functional group
3640–3610 (s, sh) O–H stretch, free hydroxyl alcohols, phenols
3500–3200 (s,b) O–H stretch, H–bonded alcohols, phenols
primary, secondary amines,
3400–3250 (m) N–H stretch
amides
3300–2500 (m) O–H stretch carboxylic acids
–C(triple bond)C–H: C–H
3330–3270 (n, s) alkynes (terminal)
stretch
3100–3000 (s) C–H stretch, few bands aromatics
3100–3000 (m) =C–H stretch, one band alkenes
3000–2850 (m) C–H stretch alkanes
2830–2695 (m) H–C=O: C–H stretch aldehydes
2260–2210 (v) C(triple bond)N stretch nitriles
2260–2100 (w) –C(triple bond)C– stretch alkynes
1760–1665 (s) C=O stretch carbonyls (general)
1710–1690 (s) C=O stretch carboxylic acids
1745–1735 (s) C=O stretch esters, saturated aliphatic
1730–1720 (s) C=O stretch aldehydes, saturated aliphatic
1730–1715 (s) C=O stretch alpha,beta–unsaturated esters
1715 (s) C=O stretch ketones, saturated aliphatic
alpha,beta–unsaturated
1710–1665 (s) C=O stretch
aldehydes, ketones
1680–1640 (m) –C=C– stretch alkenes
1650–1580 (m) N–H bend primary amines
1600–1585 (m) C–C stretch (in–ring) aromatics
1550–1475 (s) N–O asymmetric stretch nitro compounds
1500–1400 (m) C–C stretch (in–ring) aromatics
1470–1450 (m) C–H bend alkanes
1370–1350 (m) C–H rock alkanes
1360–1290 (s) N–O symmetric stretch nitro compounds
1335–1250 (s) C–N stretch aromatic amines
alcohols, carboxylic acids,
1320–1000 (s) C–O stretch
esters, ethers

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1300–1150 (m) C–H wag (–CH2X) alkyl halides
1300–1150 (m) C–H wag (–CH2X) alkyl halides
1250–1020 (m) C–N stretch aliphatic amines
1000–650 (s) =C–H bend alkenes
950–910 (m) O–H bend carboxylic acids
910–665 (s, b) N–H wag primary, secondary amines
900–675 (s) C–H "oop" aromatics
850–550 (m) C–Cl stretch alkyl halides
725–720 (m) C–H rock alkanes
700–610 (b, s) –C(triple bond)C–H: C–H bend alkynes
690–515 (m) C–Br stretch alkyl halides

m=medium, w=weak, s=strong, n=narrow, b=broad, sh=sharp

IR Spectra of Selected Compounds

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Alkanes

The spectra of simple alkanes are characterized by absorptions due to C–H stretching and
bending (the C–C stretching and bending bands are either too weak or of too low a frequency
to be detected in IR spectroscopy). In simple alkanes, which have very few bands, each band
in the spectrum can be assigned.

 C–H stretch from 3000–2850 cm-1

 C–H bend or scissoring from 1470-1450 cm-1
 C–H rock, methyl from 1370-1350 cm-1
 C–H rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

The IR spectrum of octane is shown below. Note the strong bands in the 3000-2850 cm-1
region due to C-H stretch. The C-H scissoring (1470 cm-1), methyl rock (1383 cm-1), and
long-chain methyl rock (728 cm-1) are noted on this spectrum.

The region from about 1300-900 cm-1 is called the fingerprint region. The bands in this
region originate in interacting vibrational modes resulting in a complex absorption pattern.
Usually, this region is quite complex and often difficult to interpret; however, each organic
compound has its own unique absorption pattern (or fingerprint) in this region and thus an IR
spectrum be used to identify a compound by matching it with a sample of a known compound.

Alkenes

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Alkenes are compounds that have a carbon-carbon double bond, –C=C–. The stretching
vibration of the C=C bond usually gives rise to a moderate band in the region 1680-1640
cm-1.

Stretching vibrations of the –C=C–H bond are of higher frequency (higher wavenumber) than
those of the –C–C–H bond in alkanes.

This is a very useful tool for interpreting IR spectra: Only alkenes and aromatics show a C-H
stretch slightly higher than 3000 cm-1, alkenes typically single band at about 3080 cm-1,
aromatics few bands between 3100-3000 cm-1. Compounds that do not have a C=C bond
show C-H stretches only below 3000 cm-1.

The strongest bands in the spectra of alkenes are those attributed to the carbon-hydrogen
bending vibrations of the =C–H group. These bands are in the region 1000-650 cm-1 (Note:
this overlaps the fingerprint region).

Summary:

 C=C stretch from 1680-1640 cm-1

 =C–H stretch from 3100-3000 cm-1 (typically single band at about 3080 cm-1)
 =C–H bend from 1000-650 cm-1

The IR spectrum of 1-octene is shown below. Note the band greater than 3000 cm-1 for the
=C–H stretch and the several bands lower than 3000 cm-1 for –C–H stretch (alkanes). The
C=C stretch band is at 1644 cm-1. Bands for C–H scissoring (1465 cm-1) and methyl rock
(1378 cm-1) are marked on this spectrum.

It is interesting to overlay a spectrum of 1-octene with octane (shown below). Note how
similar they are, except for the bands due to C=C or C=C–H stretches/bends.

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Aromatics

The =C–H stretch in aromatics (usually few bands) is observed at 3100-3000 cm-1. Note that
this is at slightly higher frequency than is the –C–H stretch in alkanes.

This is a very useful tool for interpreting IR spectra: Only alkenes and aromatics show a C–H
stretch slightly higher than 3000 cm-1, alkenes typically single band at about 3080 cm-1,
aromatics few bands between 3100-3000 cm-1. Compounds that do not have a C=C bond
show C–H stretches only below 3000 cm-1.

Aromatic hydrocarbons show absorptions in the regions 1600-1585 cm-1 and 1500-1400 cm-1
due to carbon-carbon stretching vibrations in the aromatic ring.

Bands in the region 1250-1000 cm-1 are due to C–H in-plane bending, although these bands
are too weak to be observed in most aromatic compounds.

Besides the C–H stretch above 3000 cm-1, two other regions of the infrared spectra of
aromatics distinguish aromatics from organic compounds that do not have an aromatic ring:

 2000-1665 cm-1 (few weak bands known as "overtones")

 900-675 cm-1 (out-of-plane or "oop" bands)

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Not only do these bands distinguish aromatics, but they can be useful if you want to determine
the number and positions of substituents on the aromatic ring. The pattern of overtone bands
in the region 2000-1665 cm-1 reflect the substitution pattern on the ring. The pattern of the
oop C–H bending bands in the region 900-675 cm-1 are also characteristic of the aromatic
substitution pattern.

Summary:

 C–H stretch from 3100-3000 cm-1, few bands

 overtones, weak, few bands, from 2000-1665 cm-1
 C–C stretch (in-ring) from 1615-1590 cm-1
 C–C stretch (in-ring) from 1500-1400 cm-1
 C–H "oop" from 900-675 cm-1

The spectrum of toluene is shown below. Note the =C–H stretches of aromatics (3099, 3068,
3032 cm-1) and the –C–H stretches of the alkyl (methyl) group (2925 cm-1 is the only one
marked). The characteristic overtones are seen from about 2000-1665 cm-1. Also note the
carbon-carbon stretches in the aromatic ring (1614, 1506, 1465 cm-1), the in-plane C–H
bending (1086, 1035 cm-1), and the C–H oop (738 cm-1).

Alcohols

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Alcohols have characteristic IR absorptions associated with both the O-H and the C-O
stretching vibrations. When run as a thin liquid film, or "neat", the O–H stretch of alcohols
appears in the region 3500-3200 cm-1 and is a very intense, broad band. The C–O stretch
shows up in the region 1260-1050 cm-1.

 O–H stretch, hydrogen bonded 3500-3200 cm-1

 C–O stretch 1260-1050 cm-1 (s)

The spectrum of ethanol is shown below. Note the very broad, strong band of the O–H stretch
(3391 cm-1) and the C–O stretches (1102, 1055 cm-1).

Carbonyl Compounds

1. Ketones

The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears at 1715
cm-1. Conjugation of the carbonyl group with carbon-carbon double bonds or phenyl groups,
as in alpha, beta-unsaturated aldehydes and benzaldehyde, shifts this band to lower
wavenumbers, 1685-1666 cm-1.

Summary:

 C=O stretch:
o aliphatic ketones 1715 cm-1
o α, β-unsaturated ketones 1685-1666 cm-1

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The spectrum of 2-butanone is shown below. This is a saturated ketone, and the C=O band
appears at 1715 cm-1. Note the C–H stretches (around 2991 cm-1) of alkyl groups (–CH3 ). It's
usually not necessary to mark any of the bands in the fingerprint region (less than 1500 cm-1).

2. Aldehydes

The carbonyl stretch C=O of saturated aliphatic aldehydes appears from 1730-1720 cm-1. As
in ketones, if the carbons adjacent to the aldehyde group are unsaturated, this vibration is
shifted to lower wavenumbers, 1710-1685 cm-1.

Another useful diagnostic band for aldehydes is the O=C–H stretch. This band generally
appears as one or two bands of moderate intensity in the region 2830-2695 cm-1 (typically at
2720 cm-1). Since the band near 2830 cm-1 is usually indistinguishable from other C–H
stretching vibration bands (recall that the C–H stretches of alkanes appear from 3000-2850
cm-1), the presence of a moderate band near 2720 cm-1 is more likely to be helpful in
determining whether or not a compound is an aldehyde.

If you suspect a compound to be an aldehyde, always look for a peak around 2720 cm-1; it
often appears as a shoulder-type peak just to the right of the alkyl C–H stretches.

Summary:

 H–C=O stretch 2830-2695 cm-1; (typically at 2720 cm-1)

 C=O stretch:
o aliphatic aldehydes 1735-1720 cm-1
o alpha, beta-unsaturated aldehydes 1710-1685 cm-1

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The spectrum of butyraldehyde is shown below. Note the O=C–H stretches in the region
2830-2695 cm-1, especially the shoulder peak at 2725 cm-1 in butyraldehyde.

3. Esters

The carbonyl stretch C=O of aliphatic esters appears from 1750-1735 cm-1; that of α, β-
unsaturated esters appears from 1730-1715 cm-1.

The C–O stretches appear as two or more bands in the region 1300-1000 cm-1.

Summary:

 C=O stretch
o aliphatic from 1750-1735 cm-1
o α, β-unsaturated from 1730-1715 cm-1
 C–O stretch from 1300-1000 cm-1

The spectrum of ethyl acetate is shown below. Note that the C=O stretch of ethyl acetate
(1752 cm-1) is at a higher wavelength than that of the α, β-unsaturated ester ethyl benzoate
(1726 cm-1).

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4. Carboxylic Acids

Carboxylic acids show a strong, wide band for the O–H stretch. Unlike the O–H stretch band
observed in alcohols, the carboxylic acid O–H stretch appears as a very broad band in the
region 3300-2500 cm-1, centered at about 3000 cm-1. This is in the same region as the C–H
stretching bands of both alkyl and aromatic groups. Thus a carboxylic acid shows a somewhat
"messy" absorption pattern in the region 3300-2500 cm-1, with the broad O–H band
superimposed on the sharp C–H stretching bands. The reason that the O–H stretch band of
carboxylic acids is so broad is becase carboxylic acids usually exist as hydrogen-bonded
dimers.

The carbonyl stretch C=O of a carboxylic acid appears as an intense band from 1760-1690
cm-1. The exact position of this broad band depends on whether the carboxylic acid is
saturated or unsaturated, dimerized, or has internal hydrogen bonding. The C=O stretch band
of dimerized aliphitic acid is typically localized between 1720-1710 cm-1.

The C–O stretch appears in the region 1320-1210 cm-1, and the O–H bend is in the region
1440-1395 cm-1 and 950-910 cm-1, although the 1440-1395 band may not be distinguishable
from C–H bending bands in the same region.

Summary:

 O–H stretch from 3300-2500 cm-1

 C=O stretch from 1760-1690 cm-1 (aliphatic: typically localized between 1720-1710
cm-1)
 C–O stretch from 1320-1210 cm-1
 O–H bend from 1440-1395 and 950-910 cm-1

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The spectrum of hexanoic acid is shown below. Note the broad peak due to O–H stretch
superimposed on the sharp band due to C–H stretch. Note the C=O stretch (1721 cm-1), C–O
stretch (1296 cm-1), O–H bends (1419, 948 cm-1).

Amines

The N–H stretches of amines are in the region 3300-3000 cm-1. These bands are weaker and
sharper than those of the alcohol O–H stretches which appear in the same region. In primary
amines (RNH2), there are two bands in this region, the asymmetrical N–H stretch and the
symmetrical N–H stretch.

Secondary amines (R2NH) show only a single weak band in the 3300-3000 cm-1 region, since
they have only one N–H bond. Tertiary amines (R3N) do not show any band in this region
since they do not have an N–H bond.

(A shoulder band usually appears on the lower wavenumber side in primary and secondary
liquid amines arising from the overtone of the N–H bending band: this can confuse
interpretation.)

The N–H bending vibration of primary amines is observed in the region 1650-1580 cm-1.
Usually, secondary amines do not show a band in this region and tertiary amines never show a

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band in this region. (This band can be very sharp and close enough to the carbonyl region to
cause students to interpret it as a carbonyl band.)

Another band attributed to amines is observed in the region 910-665 cm-1. This strong, broad
band is due to N–H wag and observed only for primary and secondary amines.

The C–N stretching vibration of aliphatic amines is observed as medium or weak bands in the
region 1250-1020 cm-1. In aromatic amines, the band is usually strong and in the region 1335-
1250 cm-1.

Summary:

 N–H stretch 3400-3250 cm-1

o 1° amine: two bands from 3400-3300 and 3330-3250 cm-1
o 2° amine: one band from 3350-3310 cm-1
o 3° amine: no bands in this region
 N–H bend (primary amines only) from 1650-1580 cm-1
 C–N stretch (aromatic amines) from 1335-1250 cm-1
 C–N stretch (aliphatic amines) from 1250–1020 cm-1
 N–H wag (primary and secondary amines only) from 910-665 cm-1

The spectrum of aniline is shown below. This primary amine shows two N–H stretches (3442,
3360); note the shoulder band, which is an overtone of the N–H bending vibration. The C–N
stretch appears at 1281 rather than at lower wavenumbers because aniline is an aromatic
compound. Also note the N–H bend at 1619.

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Nitro Groups

The N–O stretching vibrations in nitroalkanes occur near 1550 cm-1 (asymmetrical) and 1365
cm-1 (symmetrical), the band at 1550 cm-1 being the stronger of the two. Actually, both the
bands are very strong in comparison to the bands of other functional groups.

If the nitro group is attached to an aromatic ring, the N–O stretching bands shift to down to
slightly lower wavenumbers: 1550-1475 cm-1 and 1360-1290 cm-1.

Summary:

 N–O asymmetric stretch from 1550-1475 cm-1

 N–O symmetric stretch from 1360-1290 cm-1

See spectrum of m-nitrotoluene below. In nitrotoluene, the N–O stretches are at 1537 cm-1 and
1358 cm-1.

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