IR Spectroscopy

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 • Intensity of absorption
* polar nature depends on polarity of bonds
• Non-polar molecules do not
* dipole moment exhibit IR spectra due to
* partial charges absence of dipoles
* Absorption of IR radiation • Existence of H bonds can be
detected
* Electric f ield of IR radiations excite •
H bond between hydroxyl
the vibrational energy of molecule at groups changes the OH
different rate of vibration vibrations
* Change in dipole moment & hence IR • Molecules with several bonds
vibrate to different
active extent(finger print region 500
* close packed absorption bands 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, CH COOCH CH
3 2 3

C-H

C= “fingerprint
O 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
 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

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

IDENTIFICATION OF PARTICULAR The presence of bonds such as O-H

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 PARTICULAR The presence of bonds such as O-H

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 COMPOUNDS The only way to completely identify a

BY DIRECT COMPARISON OF compound using IR is to compare its
SPECTRA 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

AND
CARBOXYLIC ACID
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
 INFRA RED
SPECTROSCOPY
 KNOCKHARDY PUBLISHING

INFRA RED SPECTROSCOPY

INTRODUCTION
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INFRA RED SPECTROSCOPY
CONTENTS
• Prior knowledge
• Origins of infra red spectra
• Vibrations of bonds in molecules
• The Infra Red spectrophotometer
• Uses of IR
• Interpretation of IR spectra
• Characteristic absorption frequencies
• Check list
INFRA RED SPECTROSCOPY
Before you start it would be helpful to…

• know the names and structures of organic functional groups

 INFRA RED SPECTROSCOPY

Different covalent bonds have different strengths due to the

masses of different atoms at either end of the bond.

As a result, the bonds vibrate at different frequencies

The frequency of vibration can be found by detecting when the

molecules absorb electro-magnetic radiation.

Various types of vibration are possible.

 INFRA RED SPECTROSCOPY

Different covalent bonds have different strengths due to the

masses of different atoms at either end of the bond.

As a result, the bonds vibrate at different frequencies

The frequency of vibration can be found by detecting when the

molecules absorb electro-magnetic radiation.

Various types of vibration are possible.

Examples include... STRETCHING and BENDING

SYMMETRIC BENDING ASYMMETRIC

STRETCHING STRETCH
BENDING AND STRETCHING IN WATER MOLECULES

SYMMETRIC STRETCHING
BENDING AND STRETCHING IN WATER MOLECULES

ASYMMETRIC STRETCHING
BENDING AND STRETCHING IN WATER MOLECULES

BENDING
 The Infra-red Spectrophotometer

• a beam of infra red radiation is passed through the sample

• a similar beam is passed through the reference cell
• the frequency of radiation is varied
• bonds vibrating with a similar frequency absorb the radiation
• the amount of radiation absorbed by the sample is compared with the reference
• the results are collected, stored and plotted
 The Infra-red Spectrophotometer

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

normal vibration vibration having absorbed energy

 INFRA RED SPECTRA - USES

IDENTIFICATION OF PARTICULAR The presence of bonds such as O-H

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 PARTICULAR The presence of bonds such as O-H

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 COMPOUNDS The only way to completely identify a

BY DIRECT COMPARISON OF compound using IR is to compare its
SPECTRA 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 different vibrations taking place
in each molecule.
 INFRA RED SPECTRA - INTERPRETATION

Infra-red spectra are complex due to the many different vibrations taking place
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.
 INFRA RED SPECTRA - INTERPRETATION

Infra-red spectra are complex due to the many different vibrations taking place
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.
The technique is useful when used in conjunction with other methods -nuclear
magnetic resonance spectroscopy and mass spectroscopy.
 INFRA RED SPECTRA - INTERPRETATION

Infra-red spectra are complex due to the many different vibrations taking place
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.
The technique is useful when used in conjunction with other methods -nuclear
magnetic resonance 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
 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 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
 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

AND
CARBOXYLIC ACID
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