IR SPECTROSCOPY

Part 2/3
IB CHEMISTRY
Understanding IR region & spectra (vibrational & rotational spectra)
• IR spectra is used to identify functional groups
• IR region extends from wave number of 600 cm-1 to 4000 cm-1
• IR radiations is not energetic to excite the electron to higher level but can bring
about changes in vibrational motions.
• Vibrational motion in a molecule depends on 1) Bond strength 2) mass of atom
• Two types of vibrational motions exists namely -
Reason for IR spectra
* polar nature
* dipole moment
* partial charges
* Absorption of IR radiation
* Electric field of IR radiations excite
the vibrational energy of molecule at
different rate of vibration
* Change in dipole moment & hence
IR active
* close packed absorption bands
• Intensity of absorption depends on
polarity of bonds
• Non-polar molecules do not exhibit
IR spectra due to absence of
dipoles
• Existence of H bonds can be
detected
• H bond between hydroxyl groups
changes the OH vibrations
• Molecules with several bonds
vibrate to different extent(finger
print region 500 cm-1 to 1500 cm-
1)
 FINGERPRINT REGION

• organic molecules have a lot of C-C and C-H bonds within their structure
• spectra obtained will have peaks in the 1400 cm -1 to 800 cm-1 range
• this is referred to as the “fingerprint” region
• the pattern obtained is characteristic of a particular compound the frequency

of any absorption is also affected by adjoining atoms or groups.

IR spectrum of ethyl ethanoate, CH3COOCH2CH3

C-H

C=O “fingerprint region”

• The energy needed to excite the bonds in a molecule and so make them vibrate
with greater amplitude, occurs in the IR region.

• A bond will only interact with the electromagnetic infrared radiation, however, if it is
polar. The presence of separate areas of partial positive and negative charge in a
molecule allows the electric field component of the electromagnetic wave to excite
the vibrational energy of the molecule.

• The change in the vibrational energy produces a corresponding change in the

dipole moment of the molecule. The intensity of the absorptions depends on the
polarity of the bond. Symmetrical non-polar bonds in N≡N and O=O do not absorb
radiation, as they cannot interact with an electric field.

A bond will absorb radiation of a frequency similar to its vibration(s)

normal vibration vibration having absorbed energy

Stretching in Stretching & bending in poly atomic molecules
hydrogen halides
• Only stretching
motions
• HCl has higher
frequency than
HBr due to ……
energy & lower
relative atomic
mass

Ability of carbon
dioxide to absorb &
re-emit IR makes it
effective heat trapping
green house gas
 Vibrations of H2O, SO2 & CO2
Molecule Asymmetrical Symmetrical Symmetrical
stretching stretching bending
- - -
O O O
H2O +
H H + +
H H + +
H H +
IR active IR active IR active

+ + +
S S S
SO2 -
O O - -
O O - - O O -
IR active IR active IR active

- + - - + - - + -
CO2 O C O O C O O C O
IR active IR inactive IR active
 INFRA RED SPECTRA - USES

IDENTIFICATION OF The presence of bonds such as O-H

PARTICULAR BONDS and C=O within a molecule can be
IN A MOLECULE confirmed because they have
characteristic peaks in identifiable
parts of the spectrum.
 INFRA RED SPECTRA - USES

IDENTIFICATION OF The presence of bonds such as O-H

PARTICULAR BONDS and C=O within a molecule can be
IN A MOLECULE confirmed because they have
characteristic peaks in identifiable
parts of the spectrum.

IDENTIFICATION OF The only way to completely identify

COMPOUNDS BY DIRECT a compound using IR is to compare
COMPARISON OF SPECTRA its spectrum with a known sample.
The part of the spectrum known as
the ‘Fingerprint Region’ is unique to
each compound.
 INFRA RED SPECTRA - INTERPRETATION

Infra-red spectra are complex due to the many vibrations in each molecule.
Total characterisation of a substance based only on its IR spectrum is almost
impossible unless one has computerised data handling facilities for comparison of
the obtained spectrum with one in memory.
However, the technique is useful when used in conjunction with other methods
such as nuclear magnetic resonance (nmr) spectroscopy and mass spectroscopy.

Peak position depends on bond strength

masses of the atoms joined by the bond

strong bonds and light atoms absorb at lower wavenumbers

weak bonds and heavy atoms absorb at high wavenumbers

 INFRA RED SPECTRA - INTERPRETATION

Vertical axis Absorbance the stronger the absorbance the larger the peak

Horizontal axis Frequency wavenumber (waves per centimetre) / cm-1

Wavelength microns (m); 1 micron = 1000 nanometres
 IR SPECTRUM OF A CARBONYL COMPOUND

• carbonyl compounds show a sharp, strong absorption between 1700 and 1760 cm -1
• this is due to the presence of the C=O bond
 IR SPECTRUM OF AN ALCOHOL

• alcohols show a broad absorption between 3200 and 3600 cm -1

• this is due to the presence of the O-H bond
 IR SPECTRUM OF A CARBOXYLIC ACID

• carboxylic acids show a broad absorption between 3200 and 3600 cm -1

• this is due to the presence of the O-H bond
• they also show a strong absorption around 1700 cm -1
• this is due to the presence of the C=O bond
 IR SPECTRUM OF AN ESTER

• esters show a strong absorption between 1750 cm -1 and 1730 cm-1

• this is due to the presence of the C=O bond
NOTE
• Lighter atoms vibrate at high frequency
• Multiple bonds vibrate at higher frequency than single bonds
• HCl vibrates at higher frequency than HBr or HI
• Which requires more energy/more frequency?
• Aldehyde and ketone cannot be distinguished
• 100% transmittance is no absorption & 0% transmittance is total
absorption
• General approach to analysing infrared spectra
■ Examine the spectrum from left to right, starting at 4000 cm–1.
■ Note which are the strongest absorptions and attempt to match
them to the data book let
■ Note any absence of peaks in important areas.
■ Do not attempt to match all the peaks, especially in the
fingerprint region.
IR spectrum of ethanol, CH3CH2OH
Propanone
• The baseline at the top corresponds to 100% transmittance and
the key features are the troughs which occur at the natural
frequencies of the bonds present in the molecule.
• The absorption at just below 1800 cm–1 shows the presence of
the C= O bond and the absorption near 3000 cm–1 is due to the
presence of the C– H bond. The more polar C= O bond produces
the more intense absorption.
Ethanol
• The presence of the C–H bond can again been seen near 3000
cm–1 in the spectrum of ethanol.
• The broad peak at just below 3400 cm–1 shows the presence of
hydrogen bonding which is due to the hydroxyl (OH) group.
 WHAT IS IT!

One can tell the difference between alcohols, aldehydes and

carboxylic acids by comparison of their spectra.

O-H STRETCH ALCOHOL

C=O STRETCH ALDEHYDE

O-H STRETCH
CARBOXYLIC ACID
AND

C=O STRETCH
 CHARACTERISTIC FREQUENCIES

N-H CN C-Cl

O-H C=O C-O

C-H Aromatic C-C

C=C C-C alkanes

 CHARACTERISTIC ABSORPTION FREQUENCIES

Bond Class of compound Range / cm-1 Intensity

C-H Alkane 2965 - 2850 strong
C-C Alkane 1200 - 700 weak
C=C Alkene 1680 - 1620 variable

C=O Ketone 1725 - 1705 strong

Aldehyde 1740 - 1720 strong
Carboxylic acid 1725 - 1700 strong
Ester 1750 - 1730 strong
Amide 1700 - 1630 strong
C-O Alcohol, ester, acid, ether 1300 - 1000 strong

O-H Alcohol (monomer) 3650 - 3590 variable, sharp

Alcohol (H-bonded) 3420 - 3200 strong, broad
Carboxylic acid (H-bonded) 3300 - 3250 variable, broad

N-H Amine, Amide 3500 (approx) medium

CN Nitrile 2260 - 2240 medium

C-X Chloride 800 - 600 strong

Bromide 600 - 500 strong
Iodide 500 (approx) strong