Download Details IR CH143 2011

Infra Red spectroscopy
CH143 executive summary
• Use to Pharmaceutical analysis (Watson
Chapter 5).
• Structural elucidation.
• Finger print region.
• Video’s at
– http://www.youtube.com/watch?v=iR056lpileE
INFRA RED SPECTROSCOPY
Slide courtesy of Knockhardy Publishing
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
STRETCHING
BENDING
ASYMMETRIC
STRETCH
Types of Functional Groups
Example of a IR Spectrum
100
80
O
60
CH3O C CH2CH2CH2CH3
40
C-O
C=O
20
3500
3000
2500
2000
1500
C-O stretching at 1300-1000 cm-1 (strong)
C=O stretching near 1735 cm-1
1000
500
Slide courtesy of Knockhardy Publishing
BENDING AND STRETCHING IN WATER MOLECULES
SYMMETRIC STRETCHING
Slide courtesy of Knockhardy Publishing
BENDING AND STRETCHING IN WATER MOLECULES
ASYMMETRIC STRETCHING
Slide courtesy of Knockhardy Publishing
BENDING AND STRETCHING IN WATER MOLECULES
BENDING
Slide courtesy of Knockhardy Publishing
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
JOG 2008
Slide courtesy of Knockhardy Publishing
The Infra-red Spectrophotometer
A bond will absorb radiation of a frequency similar to its vibration(s)
normal vibration
vibration having absorbed energy
Slide courtesy of Knockhardy Publishing
INFRA RED SPECTRA - USES
IDENTIFICATION OF
PARTICULAR BONDS
IN A MOLECULE
The presence of bonds such as O-H
and C=O within a molecule can be
confirmed because they have
characteristic peaks in identifiable
parts of the spectrum.
IDENTIFICATION OF
COMPOUNDS BY DIRECT
COMPARISON OF SPECTRA
The only way to completely identify
a compound using IR is to compare
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
Slide courtesy of Knockhardy Publishing
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
Slide courtesy of Knockhardy Publishing
INFRA RED SPECTRA - INTERPRETATION
Vertical axis
Absorbance
the stronger the absorbance the larger the peak
Horizontal axis
Frequency
Wavelength
wavenumber (waves per centimetre) / cm-1
microns (m); 1 micron = 1000 nanometres
Slide courtesy of Knockhardy Publishing
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.
Slide courtesy of Knockhardy Publishing
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
Slide courtesy of Knockhardy Publishing
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
Slide courtesy of Knockhardy Publishing
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
Slide courtesy of Knockhardy Publishing
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?
Slide courtesy of Knockhardy Publishing
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
Slide courtesy of Knockhardy Publishing
CHARACTERISTIC FREQUENCIES
N-H
O-H
C-H
CN
C-Cl
C=O
C-O
Aromatic C-C
C=C
C-C alkanes
Slide courtesy of Knockhardy Publishing
CHARACTERISTIC ABSORPTION FREQUENCIES
Bond
Class of compound
Range / cm-1
Intensity
C-H
C-C
C=C
Alkane
Alkane
Alkene
2965 - 2850
1200 - 700
1680 - 1620
strong
weak
variable
C=O
Ketone
Aldehyde
Carboxylic acid
Ester
Amide
Alcohol, ester, acid, ether
1725 - 1705
1740 - 1720
1725 - 1700
1750 - 1730
1700 - 1630
1300 - 1000
strong
strong
strong
strong
strong
strong
O-H
Alcohol (monomer)
Alcohol (H-bonded)
Carboxylic acid (H-bonded)
3650 - 3590
3420 - 3200
3300 - 3250
variable, sharp
strong, broad
variable, broad
N-H
CN
Amine, Amide
Nitrile
3500 (approx)
2260 - 2240
medium
medium
C-X
Chloride
Bromide
Iodide
800 - 600
600 - 500
500 (approx)
strong
strong
strong
C-O
Quick Test 1
• The fingerprint region is made use of in
which of the following techniques?
A)UV spectroscopy.
B)Gas analysis.
C)Fluorescence spectroscopy.
D)IR spectroscopy to confirm structure.
Quick Test 2
• A compound has undergone a transformation to
an ester from a carboxylic acid. Which of the
following would be expected in the IR spectrum?
A)The spectra would be identical.
B)There would be a hydroxyl absorption around
3500 cm-1 in the acid that would not be seen in
the ester spectrum.
C)The fingerprint region would be missing from the
spectrum.
D)The carbonyl absorption would disappear.
Quick test 3
• A carbonyl group has a characteristic stretch
around 1700 cm-1 in the infra red spectrum.
Which of the following types of compounds has
this functional group?
•
•
•
•
A)
B)
C)
D)
Alkanes
Esters
Amines
Alkenes
Quick test 4
1. When using spectroscopy techniques to identify
the structure of a drug molecules it is important to
•
a. Only ever use titrations, no other techniques have any
merit.
b. Never use I.R spectroscopy.
c. Use as many spectroscopic techniques as possible
including UV and IR spectroscopy.
d. Rely up fluoresces spectroscopy only.
e. Never use a fingerprint region associated with I.R.
spectroscopy.