IR Spectra Analysis

Primciple of IR

Energies in infra-red radiation correspond to the energies involved in

bond vibrations.
That is molecules absorb IR radiation when bonds undergo stretching
and bending vibrations transitions.
Vibrational transitions- movement from lower to higher vibrational
states
Types of molecules that are IR active

 Molecules which have a dipole

 Molecules that bring about a change in the dipole moment
 Dipole is formed when molecules within a covalent bond share the
electrons unequally
Absorption of IR Radiation

The energy absorbed/involved in this vibration depends on things like:

 (1) the length of the bond and
 (2) the mass of the atoms at either end That means that each different bond
will vibrate in a different way, involving different amounts of energy.
each different bond will absorb a different frequency (and hence energy) of
infra-red radiation.
Nature of Covalent bonds

 In covalent bonds, atoms are not joined by rigid links

 the two atoms are held together because both nuclei are attracted to
the same pair of electrons
 The two nuclei can vibrate backwards and forwards - towards and
away from each other - around an average position
Types of Vibrations

Stretching vibrations
The two nuclei involved in a covalent bond can vibrate backwards and forwards - towards and away
from each other - around an average position.

Bending vibrations- the bond angles within a covalent molecule fluctuates slightly
around its average value
Vibrational Modes

  CO2 SO2
Type of molecule linear Non-linear
Polar vs non-polar Non-polar polar
Vibrational mode (symmetric stretch) Non IR active IR active

Vibrational mode (asymmetric stretch) IR active IR active

Vibrational mode IR active IR active

(bending)
Uses of IR spectroscopy

 Determination/ Identification of functional groups

 the monitoring of air pollutants examples carbon dioxide and sulphur
dioxide
 forensic analysis
 Determine the degree of unsaturation in polymers
Sample Preparation IR –solid samples
Method1

Crush the sample with a mulling agent (usually Nujol) in a

marble or agate mortar, with a pestle.
A thin film of the mull is applied onto salt plates made of
sodium chlorides and place in sample holder for analysis
Sample Preparation IR –solid samples
Method 2

 Grind a quantity of the sample with a specially purified salt (usually

potassium bromide) finely (to remove scattering effects from large
crystals).
 This powder mixture is then crushed in a mechanical die press to form
a translucent pellet
 Pellet is placed in the sample holder through which the beam of the
spectrometer can pass.
Sample Preparation IR – liquid samples

 Liquid samples can be sandwiched between two plates of a high

purity salt (commonly sodium chloride, or common salt, although a
number of other salts such as potassium bromide or calcium fluoride
are also used).
 The plates are transparent to the infrared light and will not introduce
any lines onto the spectra. Some salt plates are highly soluble in
water, so the sample and washing reagents must be anhydrous
(without water).
 CHARACTERISTIC INFRARED ABSORPTION FREQUENCIES
Bond Compound Type Frequency range, cm-1
2960-2850(s) stretch
Alkanes
C-H 1470-1350(v) scissoring and bending
CH3 Umbrella Deformation 1380(m-w) - Doublet - isopropyl, t-butyl
3080-3020(m) stretch
C-H Alkenes
1000-675(s) bend
Aromatic Rings 3100-3000(m) stretch
C-H Phenyl Ring Substitution Bands 870-675(s) bend
Phenyl Ring Substitution Overtones 2000-1600(w) - fingerprint region
3333-3267(s) stretch
C-H Alkynes
700-610(b) bend
C=C Alkenes 1680-1640(m,w)) stretch
CºC Alkynes 2260-2100(w,sh) stretch
C=C Aromatic Rings 1600, 1500(w) stretch
C-O Alcohols, Ethers, Carboxylic acids, Esters 1260-1000(s) stretch
C=O Aldehydes, Ketones, Carboxylic acids, Esters 1760-1670(s) stretch
Monomeric -- Alcohols, Phenols 3640-3160(s,br) stretch
O-H Hydrogen-bonded -- Alcohols, Phenols 3600-3200(b) stretch
Carboxylic acids 3000-2500(b) stretch
3500-3300(m) stretch
N-H Amines
1650-1580 (m) bend
C-N Amines 1340-1020(m) stretch
CºN Nitriles 2260-2220(v) stretch
1660-1500(s) asymmetrical stretch
NO2 Nitro Compounds
1390-1260(s) symmetrical stretch
Interpretation of IR Spetra

IR is not generally used to determine the whole structure of

an unknown molecule.
We don’t need to analyze every single peak   
Instead, IR is great for identifying certain specific functional
groups,
The peaks represent areas of the spectrum where specific bond vibrations occur. The following gives an
overview of the IR window from 4000 cm -1 to 500 cm -1 with various regions of interest
highlighted.
OH Stretch in ALCOHOLS
OH Stretch in CARBOXYLIC ACIDSHydroxyl
groups in carboxylic acids are considerably broader than in alcohols
 C=O peaks, in the region around 1630-1800
cm -1
The C-H Stretch Boundary at 3000 cm-1
 N-H Stretch Amines and Amides
the primary amine and primary amide have two “fangs”, while the secondary amine and secondary
amide have a single peak.
The amine stretches tend to be sharper than the amide stretches; also the amides can be distinguished by
a strong C=O stretch
Answer- Problem 1

The band at 1716 indicates a carbonyl, probably a ketone.

The bands at 3000-2850 indicate C-H alkane stretches .
Problem 2
Answer- Promlem 2

OH stretch and CH stretch no carbonyl group

therefore an ALCOHOL
Problem 3
Answer- Problem 3

OH stretch, C=O stretch and sp3 CH stretch therefore

CARBOXYLIC ACID
Problem 4
Answer- Problem 4

Sp3 CH stretch just below 3000 and C=O at around

1700 hence CARBONYL COMPOUND
Problem 5
Answer- Problem 5

 The two bands at 3433 and 3354 indicate a PRIMARY AMINE (-

NH2). The bands at 3000-2850 indicate C-H alkane stretches
Problem 6
Answer- Problem 6

 The bands at 3000-2850 indicate C-H alkane stretches. There really

aren't many other bands in the spectrum to indicate functional groups
therefore ALKANE
Reference

 Master Organic Chemistry

https://www.masterorganicchemistry.com/2016/11/23/quick_analysis_of_ir_spectra/
 Organic Chemistry from CU Boulder http://www.orgchemboulder.com/Spectroscopy/Problems/index.shtml