CHM 622

ORGANIC SPECTROSCOPY

CHAPTER 2:
APPLICATION OF
INFRARED
SPECTROSCOPY

Dr. Siti Nor Atika Baharin

 LEARNING OUTCOME

 At the end of the lesson student should be able to:

Interpret FTIR spectra and predict the unknown

compound based on spectra given
WHAT WILL WE LEARN THROUGHOUT
THIS TOPIC??

2.1 Correlation Charts and Tables

2.2 Approaching the Analysis of A Spectrum
2.3 A Survey of The Important Functional
Groups with Examples
2.4 Factors That Influence the C=O
Stretching Vibration
2.5 Infrared Problems
 INTRODUCTION

 Refer Table 2.1

 ENERGY TRANSITION IN EACH
SPECTRUM REGION

Region of Spectrum Energy Transition

X-Ray Bond Breaking
Ultraviolet/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radiofrequency Nuclear spin (nuclear magnetic
resonance)
Electronic spin (electronic spin
resonance)

Unit used wavenumber (Ṽ ), cm-1. Wavenumber (Ṽ ), cm-1

Ṽ(cm-1) = 1/λ (cm) Range: 4000-400 cm-1
v(Hz)= Ṽ c= c(cm/sec)/ λ (cm) For wavelength
# higher wavenumber corresponds to higher Range: 2.5-25 microm
energy
HOW DOES IT WORK???
 Molecules exited to Bond in most covalent
Molecule only absorbs
higher energy state, molecules vibrate
selected frequency/
when absorb IR (stretching and
energy of IR radiation
radiation bending)

Frequencies (IR
Bond must have dipole Energy absorbed – radiation) match with
moment (charge- increase amplitude of natural vibrational
capable to absorb IR vibrational motion of frequencies
radiation) the bond in molecules (molecules) are
absorbed

WHY Symmetric or pseudosymmetric compound will not absorb

IR radiation???
 Infra red spectrum
– the plot of absorptions (or peaks)
intensity versus wavenumber (cm-1)
- % transmittance vs wavenumber (cm-1)
- % transmittance is how much of a particular
frequency gets through the compound.
- eg: 100% transmittance – all frequency passed straight through
the compound without any being absorbed.
-Eg: 5% transmitted – nearly all of that particular frequency is
absorbed by the compound.
-Range : 4000 cm-1 – 400 cm-1.
-IR spectrum from 1500 cm-1 to around 400 cm-1 is called
fingerprint region.
-Most functional groups have characteristic IR absorption that
do not change from one compound to another.
 SO KNOW WHAT IS THE PURPOSE
OF IR STUDIES?

Can be used as finger print for molecules

Determine structure information about a

molecules
 TYPES OF VIBRATIONS
(EFFECT TO FREQUENCY)

Stretching higher than

bending

Assymmetric higher
than symmetric
CORRELATION CHARTS AND TABLE
 BOND PROPERTIES &
ABSORPTION TRENDS
Resonance
1. force constant (K) 2. Atomic mass
# Higher K, increase (strength &
Hybridization length = affect #atom with
energy, higher higher atomic
frequencies (affects K) K)
mass= lower
# higher K= stronger #Bonds are # ketone
bond conjugated frequency (C-
stronger in C)
#triple>double>single order with C=C, the
#stretching motion> sp>sp2>sp3 C=O of ketone #lighter
bending motion will observed atom=higher
at lower frequency (C-
frequency
H)
Why???
INSTRUMENTATION
 PREPARATION OF SAMPLES

Liquid sample

Solid sample
 INTERPRETING IR SPECTRA

The plot of absorption intensity vs wavenumber – infrared spectrum

Examples of IR spectrum-octane
 INTERPRETING IR SPECTRA

IR spectrum of toluene (methylbenzene)

 Find and list all major peaks and their frequency- please
refer to correlation chart
APPROACHING THE ANALYSIS OF A
SPECTRUM

 For unknown – firstly, determine the presence of major

functional groups such as C=O, O-H, N-H, C-O, C=C,
C≡C, C≡N, NO2 in the IR spectrum.

1. C=O is present?
2. C=O is absent?
(acid, amides, 3. Double bond?
Alcohol, phenol,
ester, anhydrides,
amines, ether
aldehydes)

4. Triple 5. Nitro 6.
bond groups Hydrocarbon
 INTERPRETING IR SPECTRA
 Alkanes (molecular mass = 142 g/mol)
 C-H stretching – 3000 cm-1
 CH2 – bending – 1465 cm-1
 CH3 – bending – 1375 cm-1
 CH2 – bending –long chain band – 720 cm-1
 Alkenes
 =C-H –sp2 C-H stretch – 3095-3010; bending – 1000-650 cm-1
 C=C – stretching – 1660-1600 cm-1; cis disubstituted showed
higher absorption (stronger) than trans disubstituted.
 conjugation moves C=C stretch to lower frequency.
 Continue..
 Alkynes
 ≡C-H ~ stretch for sp C-H near 3000 cm-1
 C≡C ~ stretch near 2150 cm-1
Alcohols
 Free O-H stretch ~ sharp peak at 3650 – 3600 cm-1
 Hydrogen-bonded O-H ~ broad band at 3400 – 3300 cm-1
 C-O-H bending ~ broad and weak peak at 1440 – 1220 cm-1
 C-O stretch ~ peak at the area of 1260 – 1000 cm-1
 CH3(CH2)4CH2OH
Ether (R-O-R)
 C-O stretch – 1300 -1000 cm-1
 Phenyl alkyl ether – strong band at 1250 – 1040 cm-1
 Aliphatic ethers – strong band at 1120 cm-1
Aromatic
 =C-H : absorption peak greater than 3000 cm-1 (3.50-3.10 cm-1).
Stretching for sp2 C-H
 =C-H : absorption at 900-690 cm-1 for oop bending. Important to
assign the ring substitution.
 C=C : absorption peaks (in pair) at 1600 cm-1 and 1475 cm-1.
 Overtone/combination bands between 2000 cm-1 and 1667 cm-1 also
can be used to assign the ring substitution pattern.
Aldehydes
 Strong (sharp) absorption in the range 1740-1725 cm-1 is for the C=O in
simple aldehyde. If conjugation with C=C or phenyl group the band shifts
to lower frequency.
 Absorption peak at 2850 and 2750 cm-1 are for C-H stretching for
aldehyde. Doublet sharp peaks.
 Doublet peaks can be used to distinguish aldehyde with other carbonyl-
containing compound.
 Continue…
Ketone
 Strong absorption peak in the range 1720-1708 cm-1 is for C=O group in
simple aliphatic ketone. Conjugation with C=C and and phenyl group shifts
the band to lower frequency.
 An α-halogen atom will increase the absorption frequency of C=O
 Ring strain causes C=O shows higher absorption frequency in cyclic ketone
Carboxylic acid
 O-H group : absorption peak occurs at 3400-2400 cm-1 . Stretching. Very
broad peak. Often overlaps with C-H absorptions.
 C=O group : Absorption peak 1730-1700 cm-1. Stretching vibration.
Broad peak. Conjugation lowers the frequency.
 C-O group : Absorption peak in the range of 1320-1210 cm-1. Stretching
vibration. Medium intensity.
Ester
 Very strong absorption peak in the range 1750-1735 cm-1 is for C=O group
for simple aliphatic esters. The peak shifted to lower frequency if
conjugation occurs with C=C or phenyl groups.
 Conjugation of C=C with single-bonded-oxygen (C-O) in an ester
increased frequency to higher value from the range given.
 Ring strain causes C=O shows higher absorption frequency in cyclic
esters.
Amides
 C=O group : Stretching vibration in the range 1680-1630 cm-1.
 N-H group : Stretching vibration – (-NH2) at near 3350 cm-1 and at 3180
cm-1. For (-NH) one band at 3300 cm-1.
 N-H group : bending vibration at around 1640-1550 cm-1 for –NH2 and –
NH amides.
Amines
 N-H group : Stretching vibration. primary amines (R-NH2) shows two
absorption peaks in range 3500-3300 cm-1. One peak(band) for secondary
amine (R2N-H) in the region.
 No N-H stretching for tertiary amine (R3N)
 N-H stretching can be used to differentiate between primary, secondary
and tertiary amine.
 Continue...
LETS TRY THIS!
MW=107 g/mol

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MW=108 g/mol

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ATIKABAHARIN/UITMNS/2017