MOLECULAR ABSORPTION

SPECTROSCOPY; THEORY,
INSTRUMENTATION &
APPLICATION (CHAPTER 2)

CHM 260

MASTURA IBRAHIM
UiTM Perak (Kampus Tapah)
 2

Lesson Outcomes

•Explain the principles of molecular spectroscopy (UV, IR)

•Draw and label the schematic diagram of the instruments
in molecular spectroscopy
•Able to explain the functions of each component in each
instrument.
•Discuss the difference between each instrument in terms
of parts and functions (example radiation sources, sample
cells, wavelength selectors, beam chopper and detectors)
•Interpret analytical information from spectral data.
 3

2.1 COMPONENTS OF
INSTRUMENTAL FOR
OPTICAL SPECTROSCOPY
 4

2.1.1 General Designs of Optical

Instrument
• Absorption Spectroscopy

• Emission Spectroscopy
 5

5 Basic Optical Instrument

Components
1. Source
A stable source of radiant energy at the desired
wavelength (or λ range)
2. Sample Holder
A transparent container used to hold the sample (cells,
cuvettes, etc.)
3. Wavelength Selector
A device that isolates a restricted region of the EM
spectrum used for measurement (monochromators,
prisms, & filters)
 6

4. Photoelectric Transducer (Detector)

Converts the radiant energy into a useable signal
(usually electrical)
5. Signal Processor & Readout
Amplifies or attenuates the transduced signal and sends
it to a readout device such as a meter, digital readout,
chart recorder, computer, etc.
 7

1. Radiation Sources
• Generate a beam of radiation that is stable and has
sufficient power
• 1. Continuum Sources:
Emit radiation over a broad wavelength range and the
intensity of the radiation changes slowly as a function of
wavelength.
This type of source is commonly used in UV, visible and
IR instruments
- Deuterium lamp is the most common UV source.
- Tungsten lamp is the most common visible source.
- Glowing inert solids are common sources for IR
instruments.
 8

• 2. Line Sources:
Emit a limited number lines or bands of radiation at
specific wavelength
Used in atomic absorption spectroscopy
Usually provide radiation in the UV and visible region of
the EM spectrum
Types of line source:
- Hollow cathode lamps
- Electrodeless discharge lamps
- Lasers-Light – amplification by stimulated emission of
radiation
 9

(Source: http://www.saylor.org/courses/chem108)
 10

2. Sample Containers
• Sample containers usually is called cells or cuvettes,
must have side/windows that are transparent in the
spectral region of interest.
• There are few types of cuvettes:
1. quartz or fused silica (below 350nm)
required for UV & VIS region

2. silicate glass (350 – 2000nm)

cheaper compared to quartz. used in VIS

3. crystalline sodium chloride

used in IR
 11

• Examples of sample cells for UV/Vis spectroscopy. From left to right (with path lengths in parentheses), rectangular plastic cuvette (10.0 mm), rectangular quartz cuvette (5.000 mm), rectangular quartz,
cuvette (1.000 mm), cylindrical quartz cuvette (10.00 mm), cylindrical quartz cuvette (100.0 mm). Cells often are available as a matched pair, which is important when using a double-beam instrument .
(Source: http://www.saylor.org/courses/chem108)
 12

3. Wavelength Selectors
• Wavelength selectors provides a limited, narrow,
continuous group of wavelengths called a band
• Two types of wavelength selectors:
1. Filters
- Two types of filters:
i. Interference Filters
ii. Absorption Filters

2. Monochromators
- Wavelength selector that select a specific wavelength
- Used in most scanning spectrometers
including UV, visible, and IR instruments.
 13

Schematic diagram of monochromator that uses a diffraction grating to

disperse a radiation
 14

4. Radiation Detectors &

Transducers
• Early detectors in spectroscopic instruments were the
human eye, photographic plates or films
• Modern instruments contain devices that convert the
radiation to an electrical signal
• Two general types of radiation detectors:
1. Photon detectors
2. Thermal detectors
 15

1. Photon Detectors:
- Commonly useful in ultraviolet, visible and near
infrared instruments
- Several types of photon detectors are available:
i) Vacuum phototubes
ii) Photomultiplier tubes
iii)Photovoltaic cells
iv)Silicon photodiodes
v) Diode array transducers
vi)Photoconductivity transducers
 16

1. Thermal Detectors:
- Used for infrared spectroscopy because photons in the
IR region lack the energy to cause photoemission of
electrons
- Three types of thermal detectors :
i) Thermocouples
ii) Bolometers
iii)Pyroelectric transducers
 17

Summary
 18

2.2 INSTRUMENTS FOR

OPTICAL ABSORPTION
MEASUREMENTS
 19

Info:

• SPECTROMETER
is a that employs a monochromator or polychromator in
conjunction with a transducer to convert the radiant
intensities into electrical signals.

• SPECTROPHOTOMETER
is a spectrometer that allow measurement of the ratio of
the radiant powers of two beams, a requirement to
measure absorbance (recall that A=-log Po/P)
 20

Instrumentation for UV-VIS

Spectrophotometers:

• Single-Beam Instruments
• Double-Beam instruments
• Multichannel Instruments
 21

Instruments for Optical Absorption

Measurement
• Single beam Instruments:
1. Radiation source
2. Filter/monochromator (λ selector)
3. Cells
4. Detector
5. Readout device
 22

Schematic diagram of fixed-wavelength single-beam spectrophotometer

 23

ADVANTAGES:
•Suited for quantitative absorption measurements at a
single wavelength
•Simplicity of instrumentation, low cost, ease of
maintenance

DISADVANTAGES:
• Two separate readings has to be made on the light.
This results in some error because the fluctuations in the
intensity of the light do occur in the line voltage, the power
source and in the light bulb between measurements.
• Changing of wavelength is accompanied by a change
in light intensity. Thus spectral scanning is not possible.
 24

• Double beam:
1. Radiation source
2. Filter/monochromator (λ selector)
3. Cells
4. Detector
5. Readout device
 25

• ADVANTAGES:
• Compensate for all but most short-term fluctuations in the
radiant output of the source as well as for drift in the
transducer and amplifier
• Compensate for wide variations in source intensity with λ.
• Continuous recording of transmittance or absorbance
spectra.
 26

Double beam Instrument in space:

•Beam is split into two paths and measured by matched detectors
 27

• Two beams are formed by a V-shaped mirror called a

beam spliter
- one beam passes through the reference solution to a
photodetector
- the other one simultaneously passes through the
sample to a photodetector
• Two outputs are amplified, and their ratio is computed and
displayed on the output device
 28

Double beam Instrument in time:

•Beam is split in two but measured by same detector
 29

Multichannel:
•Radiation is focused upon the sample then pasess into the
monochromator with a fixed grating.
•The dispersed radiations falls on transducer
 30

Instrumentation for IR
Spectrophotometers:

• Dispersive Instruments
• Fourier Transform Instruments (FTIR)
 31

Dispersive Instruments
• Generate a beam with sufficient power in the λ region of
interest to permit ready detection & measurement.
• Provide continuous radiation which made up of all λ’s
with the region (continuum source).
• Provide stable output for the period needed to measure
both P0 and P.
 32

Schematic Diagram of Dispersive

IR
 33

FTIR
Why FTIR is developed?
• To overcome limitations encountered with the dispersive
instruments.
• Dispersive IR spectrophotometer has slow scanning
speed due to measurement of individual molecules/atom.
• It utilize the use of an interferometer.

ADVANTAGES:
• High sensitivity, resolution,
• Simpler mechanical design
• Quick data acquisition
• More accurate wavelength calibration
• Better light-gathering power
 34

Schematic Diagram of FTIR

 35

Inferometer
• Special instrument which can read IR frequencies
simultaneously.
• Faster method than dispersive instrument.
• Interferograms are transformed into frequency
spectrums by using mathematical technique called
Fourier Transformation.

FT
Calculations

interferograms IR spectrum
 36

2.3 ULTRAVIOLET-VISIBLE
SPECTROSCOPY
 37

Organic Inorganic
compounds species

MOLECULAR SPECIES THAT

ABSORB UV/VIS RADIATION

Charge transfer
 38

Absorbing Species
• Organic compound
Chemical compound whose molecule contain carbon.
Example C6H6, C3H4
• Inorganic species
Chemical compound that does not contain carbon.
Example transition metal, lanthanide and actinide
elements
• Charge transfer
A complex where one species is an electron donor and
the other is an electron acceptor.
Example Iron(III) thiocyanate complex
 39

Principle UV-VIS Absorption

• In UV/VIS spectroscopy, molecules which absorbed the
EMR in this region will result in transitions between
electronic energy levels.
 40

• In molecules, instead
consist of electronic
level, it also comprise
of vibrational and
rotational sub-levels.
• Transitions between
these molecular
energy levels will result
in band spectra.
 41

Type of Transitions
• There are 3 types of electronic transitions
1. σ, п and n electrons
2. d and f electrons
3. Charge transfer electrons
 42

What is σ,  and n electrons?

single covalent bonds (σ)

H + O + H H O H or H O H

lone pairs(n)

O C O or O C O

double bonds ()

N N or N N

triple bond ()

 43

Sigma ()electron
• Electrons involved in single bonds such as those
between carbon and hydrogen in Alkanes.
• These bonds are called sigma, σ bonds.
• The amount of energy required to excite electrons in
σ bond is more than UV photons wavelength.
Therefore, alkanes and other saturated compounds
(compounds with only single bonds) do not absorb UV
radiation.
• As a result, Alkanes such as hexane, C6H14 are frequently
very useful as transparent solvents for the study of other
molecules.
 44

Pi () electron
• Electrons involved in double and triple bonds
(unsaturated).
• These bonds involve a п bond.
• п bond exists in alkenes, alkynes, conjugated olefins
and aromatic compounds.
• Electrons in п bonds are excited easily. These
compounds commonly absorb UV or visible photons.
 45

Organic molecules containing п bonds

H3C C C H Propyne (alkynes)

H
CH2CH3 H H
H C H
C C H C C
C C C C H
H C H
H H
H
Ethylbenzene Benzene 1,3-butadiene
(aromatics & alkenes) (conjugated olefins)
 46

Lone pair (n) electron

• Electrons that are not involved in bonding between
atoms are called n electrons.
• Organic compounds containing nitrogen, oxygen, sulfur
or halogens frequently contain electrons that are
nonbonding.
• Compounds that contain n electrons absorb UV/VIS
radiation.
 47

Organic molecules with non-bonding

electrons
NH2
H3C H
C C C
O
Br H
R
aminobenzene Carbonyl compound 2-bromopropene
 48

σ and π orbitals
 49

Electronic energy levels diagram

Unoccupied levels

Occupied levels
 50

Graphical representation of electrons in

orbitals


Unoccupied levels


Atomic orbital Atomic orbital

Energy n

Occupied levels



Molecular orbitals
 51

• In all compounds other than alkenes, the electrons may

undergo several possible transitions of different energies:


  alkanes

  carbonyls

  Unsaturated compouds.
Energy
n
n  O, N, S, halogens

n  carbonyls



 52

Absorption by Organic Compounds

• Absorption of UV/Vis by organic compounds requires that
the energy absorbed corresponds to a jump from
occupied orbital unoccupied orbital.
• Generally, the most probable transition is from the highest
occupied molecular orbital (HOMO) to the lowest
unoccupied molecular orbital (LUMO)
 53

→* transitions
• Never observed in normal UV/Vis work.
• The maximum absorption are below than 150 nm.
• The energy required to induce a σ→σ* transition is too big
(high energy) (see the arrow in energy level diagram).
• Eg:
Methane at 125 nm, Ethane at 135 nm
• This type of absorption corresponds to breaking bonds
such as C-C, C-H, C-O, C-X, ……….

σ→σ* vacuum UV region

 54

n→* transitions
• Saturated compounds that contain atoms with unshared
electron pairs.
• Compounds containing O, S, N and halogens can absorb
via this type of transition.
• Absorptions are typically in the 150 -250 nm region and
are not very intense.
• ε range: 100 – 3000 Lcm-1mol-1
• Some examples of absorption due to n→σ* transitions
 55

n→* transitions
• Unsaturated compounds containing atoms with
unshared electron pairs.
• These result in some of the most intense absorption
in 200 – 700 nm region.
• ε range: 10 – 100 Lcm-1mol-1
 56

→* transitions
• Unsaturated compounds to provide the  orbitals.
• These result in some of the most intense absorption
in 200 – 700 nm region.
• ε range: 1000 – 10,000 Lcm-1mol-1
 57

• Some examples of absorption due to n→* and →*

transitions
 58

Chromophores
• Unsaturated organic functional groups that absorb in
the UV/VIS region.
• Contains electrons with relatively low excitation
energies

Auxochromes
• Groups of atoms such as –OH, -NH2 & halogens that
attached to the double bonded atoms cause the
normal chromophoric absorption to occur at longer λ
(red shift)
59
 60

Other Factor that Influenced

Absorption
• Factors that influenced the λ:
1.Solvent effects (shift to shorter λ: blue shift)
2.Structural details of the molecules.
 61

Effect of Multichromophores on
Absorption
• More chromophores in the same molecule cause
bathochromic effect ( shift to longer ) and
hyperchromic effect (increase in intensity).
• In conjugated chromophores, * electrons are
delocalized over larger number of atoms. This cause a
decrease in the energy of →* transitions and an
increase in  due to an increase in probability for
transition.
62
 63

Important terminologies
• hypsochromic shift (blue shift)
- Absorption maximum shifted to shorter λ

• bathochromic shift (red shift)

- Absorption maximum shifted to longer λ
 64

Terminology for Absorption Shifts

65
 66

Absorption by Inorganic Species

Involving d and f electrons absorption.

1. 3d & 4d electrons
• 1st and 2nd transition metal series for example Cr, Co,
Ni & Cu.
• Absorb broad bands of VIS radiation.
• Absorption involved transitions between filled and
unfilled d-orbitals with energies that depend on the
ligands such as Cl-, H2O, NH3 or CN- which are bonded
to the metal ions.
 67

Absorption spectra of some

transition-metal ions
 68

2. 4f & 5f electrons
•Ions of lanthanide and
actinide elements.
•Their spectra consists
of narrow, well-defined
characteristic
absorption peaks.
69
 70

Charge Transfer Absorption

• Absorption involved transfer of electron from the donor
to an orbital that is largely associated with the acceptor.
• An electron occupying in a σ or  orbital (electron donor)
in the ligand is transferred to an unfilled orbital of the
metal (electron acceptor) and vice-versa.
• e.g. red colour of the iron(III) thiocyanate complex
 71

Absorption spectra by
aqueous charge
transfer complexes
 72

Quantitative Analysis
• The fundamental law on absorption methods are based
on Beer’s law (Beer-Lambert law).

• 2 types of methods:
1.Calibration curve method
2.Standard addition method
 73

How to measure the absorbance?

1. You must always attempt to work at the wavelength
of maximum absorbance, max
2. This is the point where it has the maximum
response due to better sensitivity and lower
detection limits.
3. You will also have reduced error in your
measurement when analysed the samples and
standards at max .
74
 75

Calibration Curve Method

•A general method for determining the
concentration of a substance in an unknown
sample by comparing the unknown to a set of
standard solution of known concentration.
 76

How to measure the

concentration of unknown?
•Practically, you have measure
the absorbance of your unknown.
• Once you know the absorbance
value, you can just read the
corresponding concentration from
the graph .
 77

How to produce standard

calibration curve?
1. Prepare a series of
standard solution with
known concentration.
2. Measure the absorbance
of the standard solutions.
3. Plot the graph
Absorbance vs
Concentration of the
standard solutions.
4. Find the ‘best’ straight
line by using least-
squares method.
 78

Finding the Least-Squares Line

N=5
N – is the number of points used
 79

The calculation of the slope and intercept is simplified by

defining three quantities Sxx, Syy and Sxy.

Sxx =  (xi – x)2 =  xi2– ( xi)2 ……(1)

Syy =  (yi – y)2 =  yi2– ( yi)2 ……(2)

Sxy =  (xi – x) (yi – y)2 =  xiyi –  xi  yi …(3)

 80

• The slope of the line, m:

m = Sxy
Sxx
• The intercept, b:
c = y – mx
• Thus, the equation for the least-squares line is
y = mx + c
 81

From the least-squares line equation, you can calculate the

new y values by substituting the x value.
Then plot the graph.
 82

• Most linear regression

implementations have an
option to “force the line
through the origin,” which
means forcing the
intercept of the line
through the point (0,0).
• This might seem
reasonable, since a
sample with no detectable
concentration should
produce no response in a
detector, but must be
used with care.
 83

• HOWEVER, forcing the plot through (0,0) is not

always recommended since most curves are run well
above the instrumental limit of detection (LOD).
• Randomly, adding a point (0,0) can skew the curve
because the instrument’s response near the LOD is
not predictable and is rarely linear.
 84

2.4 INFRARED ABSORPTION

SPECTROSCOPY
 85

Intro: Infrared Spectroscopy

• Infrared (IR) spectroscopy deals with the interaction of
infrared radiation with matter
• Mostly for qualitative analysis
• Absorption spectra is recorded as transmittance
• Absorption in the infrared region arise from molecular
vibrational transitions
• Absorption for every substance are at specific wavelengths
where IR spectra provides more specific qualitative
information
• IR spectra is called “fingerprints” because no other
chemical species will have similar IR spectrum
• IR spectrum provides important information about chemical
nature and structure of a molecule
•
 86

Transmittance vs Absorbance

• The transmittance
spectra provide
better contrast
between intensities
of strong and weak
bands compared to
absorbance spectra
 87

Electromagnetic Spectrum

• Energy of IR photon insufficient to cause electronic excitation but can cause vibrational excitation
 88

Vibrations

Anharmonic Oscillator
•Bond – not a perfect
Elastic nature
•Does not obey exactly
simple harmonic motion
•Dissociates
•Not a ideal parabola
 89

• IR region subdivided into 3 sub-regions:

visible
1.Near IR region (Nearest to the visible)
780 nm to 2.5 μm (12,800 to 4000 cm-1) N
E
A
R
2. Mid IR region
M
2.5 to 50 μm (4000 – 200 cm-1)

infrared
I
D

F
3. Far IR region A
R
50 to 1000 μm (200 – 10cm-1)

89

microwave
 90

When IR absorption occur?

1. IR absorption only occurs when IR radiation interacts
with a molecule undergoing a change in dipole moment
as it vibrates or rotates
2. Infrared absorption only occurs when the incoming IR
photon has sufficient energy for the transition to the
next allowed vibrational state

*No absorption can occur if both rules above are

not met!
 91

What happen when a molecule absorbs IR

radiation?
• In the absorption process, those frequencies of IR
radiation which match the natural vibrational frequencies
of the molecule are absorbed
• The energy absorbed will increase the amplitude of the
vibrational motions of the bonds in the molecule
• NOT ALL bonds in a molecule are capable of absorbing
IR energy. Only those bonds that have change in dipole
moment are capable to absorb IR radiation
• Symmetric bonds, such as H2, Cl2 do not absorb IR
• The larger the dipole change, the stronger the intensity of
the band in an IR spectrum
 92

Dipole moment
is a measure of the extent to which a separation exists
between the centers of positive and negative charge
within a molecule
 93

Molecular vibration

divided into
back & forth involves change in
movement bond angles

stretching bending

wagging
scissoring

symmetrical asymmetrical rocking twisting

out of plane
in-plane vibration
vibration
93
 94

Stretching
 95

Bending
 96

Preparation of Samples
1. Liquids:
- A drop of the pure (neat) liquid is squeezed between
two salt plates (eg: KBr, NaCl) to give a layer that has
thickness 0.01mm or less
- Neat liquid is a pure liquid that do not contain any
solvent or water
- This method is applied when the amount of liquid is
small or when a suitable solvent is unavailable
- A spectrum determined by this method is called “neat
spectrum”
- Organic compounds analysed by this method must be
free of water
 97

2. Solids:
There are 3 common methods for preparing solid samples:
i) KBr pallet:
- The finely ground solid sample is mixed KBr. The mixture
is pressed under high pressure (10,000 – 15,000 psi) in
special die to form a pellet
- Disadvantage: KBr absorbs water, thus interferes the
spectrum obtained
ii) Nujol mull:
- Involves grinding the compound with mineral oil (Nujol) to
create a suspension of finely round sample in mineral oil
and then put in between salt plates
- Disadvantage: The mineral oil obscures band that may be
present in the analyzed compound
 98

iii) Organic compound sample in solvent:

- Most commonly used solvent in this method is CCl4
- May also obscure the spectrum by bands in the
solvent
 99

KBr Pallet Method

 100

Nujol Mull Method

 101

Interpretation of IR Spectra
 102

• Steps:
1. Identify functional groups (group frequency region).
Refer to IR chart
2. Compare with standard spectra containing these
functional groups (fingerprint region)
• Fingerprint region (usually 1500-500 cm-1) contains
complicated series of absorptions due to all manner
bending vibrations within the molecule
- use in comparing compounds that contain similar bond
(eg: 1-propanol & 2-propanol)
103
104
 105

How to analyze IR spectra?

1.Begin by looking in the region from 4000-1300. Look at
the C–H stretching bands around 3000
 106

2. Look for a carbonyl in the region 1760-1690. If there is

such a band;
 107

3. Look for a broad O–H band in the region 3500-3200 cm-

1. If there is such a band

4. Look for a single or double sharp N–H band in the region

3400-3250 cm-1. If there is such a band
 108

5. Other structural features to check for

 109

• If there is an absence of major functional group bands in

the region 4000-1300 cm-1 (other than C–H stretches), the
compound is probably a strict hydrocarbon
• Also check the region from 900-650 cm-1. Aromatics, alkyl
halides, carboxylic acids, amines, and amides show
moderate or strong absorption bands (bending vibrations)
in this region

p/s:

As a beginning student, you should not try to assign or

interpret every peak in the spectrum. Concentrate on
learning the major bands and recognizing their presence
and absence in any given spectrum
 110

Alkane
CH Stretch for sp3 C-H around 3000 – 2840 cm-1.
CH2 Methylene groups have a characteristic bending absorption
at approximate 1465 cm-1
CH3 Methyl groups have a characteristic bending absorption at
approximate 1375 cm-1
CH2 The bending (rocking) motion associated with four or more
CH2 groups in an open chain occurs at about 720 cm-1
 111

Example: decane

Peak Assignment
2800 cm-1 sp3 C-H stretching
1460 cm-1 CH2 bending
1380 cm-1 CH3 bending
 112

Alkenes
=C-H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.
=C-H out-of-plane (oop) bending occurs in the range 1000 –
650 cm-1
C=C stretch occurs at 1660 – 1600 cm-1;
often conjugation moves C=C stretch to lower frequencies
and increases the intensity.
 113

Example: cyclohexene

*Peak assignment table!

 114

Alkynes
CH Stretch for sp C - H occurs near 3300 cm-1.

C C Stretch occurs near 2150 cm-1; conjugation moves stretch

to lower frequency.

Example: 1-octyne
 115

Aromatic Rings
C H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.

Ring stretch absorptions occur in pairs at 1600 cm-1

C C and 1475 cm-1.
C H Bending occurs at 900 - 690cm-1.

Example: toluene
 116

C-H Bending ( for Aromatic Ring)

The out-of-plane (oop) C-H bending is useful in order to
assign the positions of substituents on the aromatic ring:

1. Monosubstituted rings
this substitution pattern always gives a strong absorption
near 690 cm-1. If this band is absent, no monosubstituted
ring is present. A second strong band usually appears near
750 cm-1
2. Ortho-Disubstituted rings
one strong band near 750 cm-1

C H Bending observed as one strong band near 750 cm-1.

 117

3. Meta- Disubstituted rings

gives one absorption band near 690 cm-1 plus one near 780
cm-1. A third band of medium intensity is often found near
880 cm-1

C H gives one absorption band near 690 cm-1 plus one near 780
cm . A third band of medium intensity is often found near 880
-1

cm-1.

4. Para- Disubstituted rings

one strong band appears in the region from 800 to 850 cm-1

C H one strong band appears in the region from 800 to 850

cm-1.
118
 119

Alcohol
O-H The hydrogen-bonded O-H band is a broad peak at 3400 – 3300
cm-1. Free O-H stretch is a sharp peak at 3650-3600 cm-1
C-O-H Bending appears as a broad and weak peak at 1440 – 1220 cm-1
often obscured by the CH3 bendings
C-O Stretching vibration usually occurs in the range 1260 – 1000 cm-1.
This band can be used to assign a primary, secondary or tertiary
structure to an alcohol.

Example: 1-hexanol
 120

a) Free & H-bonded OH b) Free & H-bonded OH c) H-bonded OH

(very dilute solution) (dilute solution) (neat liquid)
 121

Compound C-O Stretch (cm-1) O-H Stretch (cm-1)

Phenol 1220 3610

increase
decrease
3° Alcohols (saturated) 1150 3620
2° Alcohols (saturated) 1100 3630
1° Alcohols (saturated) 1050 3640

*Unsaturation on adjacent cabons or cyclic structure lowers the frequency

of C-O absorption
 122

Ether
C-O -The most prominent band is that due to C-O stretch,
1300 – 1000 cm-1.
-Absence of C=O and O-H is required to ensure that C-O stretch
is not due to an ester or an alcohol.
-Phenyl alkyl ethers give two strong bands at about
1250 – 1040 cm-1,
while aliphatic ethers give one strong band at about 1120 cm-1.

Example: dibutyl ether

 123

Carbonyl Compound
Normal base values for the C=O stretching vibrations for carbonyl
groups:

cm-1

1810 1800 1760 1735 1725 1715 1710 1690

Anhydride Acid Anhydride Ester Aldehyde Ketone Carboxylic Amide
chloride acid
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Aldehyde
R C H
C=O stretch appear in range 1740-1725 cm-1 for
O normal aliphatic aldehydes
Ar C H Conjugation of C=O with phenyl; 1700 – 1660 cm-1 for
O C=O and 1600 – 1450 cm-1 for ring (C=C)
C-H Stretch, aldehyde hydrogen (­­-CHO), consists of weak
bands, one at 2860 - 2800 cm-1 and the other at 2760
- 2700 cm-1.
EXAMPLE:
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Ketone
R C R' C=O stretch appear in range 1720-1708 cm-1 for
O normal aliphatic ketones

Ar C R'
Conjugation of C=O with phenyl at 1700 – 1680 cm-1 for
O C=O and 1600 – 1450 cm-1 for ring (C=C)
Example: methone
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Carboxylic Acid
O-H Stretch, usually very broad (strong H-bonded, occurs at
3400-2400 cm-1 and often overlaps the C-H absorptions
C=O Stretch, broad, occurs at 1730-1700 cm-1 . Conjugation
moves the absorption to a lower frequency
C-O Stretch occurs in the range 1320-1210 cm-1 , medium
intensity
Example: pentanoic acid
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Ester
R C O R C=O stretch appear in range 1750-1735 cm-1 for normal
O aliphatic esters

Ar C O R
Conjugation of C=O with phenyl; 1740 – 1715 cm-1 for C=O
O and 1600 – 1450 cm-1 for ring (C=C)

C–O Stretch in two or more bands, one stronger and

one broader than the other,
occurs in the range 1300 – 1000 cm-1
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Amide
O O O
H H R
R C N R C N R C N
10
H R R
20
30

C=O Stretch occurs at approximately 1680-1630 cm-1

N-H Stretch in primary amides (-NH2) gives two bands
near 3350 and 3180 cm-1 . Secondary amides have
one band (-NH) at about 3300 cm-1
N-H Bending occurs around 1640-1550 cm-1 for
primary and secondary amides
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Example: propionamide
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Acid Chloride
Stretch appear in range 1810 -1775 cm-1 in
C O
conjugated chlorides. Conjugation lowers the
frequency to 1780 – 1760 cm-1
C Cl
Stretch occurs in the range 730 -550 cm-1

Acid chloride show a very strong band for the C=O group.
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Example: acetyl chloride

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Anhydride
C O Stretch always has two bands, 1830 -1800 cm-1 and 1775 –
1740 cm-1, with variable relative intensity.
Conjugation moves the absorption to a lower frequency.
Ring strain (cyclic anhydride) moves absorptions to a
higher frequency.
C O Stretch (multiple bands) occurs in the range 1300 -900 cm-1
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Amine
Stretching occurs in the range 3500 – 3300 cm-1.
N–H
Primary amines have two bands.
Secondary amines have one band, a vanishingly weak
one for aliphatic compounds and a stronger one for
aromatic secondary amines.
Tertiary amines have no N – H stretch.

N–H Bending in primary amines results in a broad band in

the range 1640 – 1560 cm-1.
Secondary amines absorb near 1500 cm-1

N–H Out-of-plane bending absorption can sometimes be

observed near 800 cm-1

C–N Stretch occurs in the range 1350 – 1000 cm-1

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Example: 1-butanamine