MOLECULAR ABSORPTION

SPECTROSCOPY; THEORY,
INSTRUMENTATION &
APPLICATION
(CHAPTER 2) – PART 4

CHM 260
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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 differences 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.
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Molecular Absorption Spectroscopy;
Theory, Instrumentation and
Application
• 2.1 Components of Instruments for Optical Spectroscopy

• 2.1.1 Optical Materials

• 2.1.2 Radiation Sources
• Continuous Sources of Visible Radiation Continuous Sources of Ultraviolet Radiation Continuous Sources
• of Infrared Radiation Line Sources
• 2.1.3 Wavelength Selectors
• 2.1.4 Radiation Detectors and Transducers
• 2.1.5 Sample Containers

• 2.2 Instruments for Optical Absorption Measurements

• 2.2.1 Ultraviolet/Visible Spectrophotometers

• Single-beam Instruments
• Double-beam Instruments
• Multichannel Instruments
• 2.2.2 Infrared Spectrophotometers
• Dispersive Instruments
• Fourier Transform Instruments
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• 2.3 Ultraviolet and Visible Spectroscopy

• 2.3.1 Molecular Species that Absorb Ultraviolet and Visible Radiation

• Absorption by Organic Compounds Absorption by Inorganic Species Charge-Transfer Absorption
• 2.3.2 Scope
• Application to Absorbing Species
• Application to Non Absorbing Species
• 2.3.3 Procedural Details
• Wavelength Selection
• Variables that influence absorbance
• Cleaning and Handling of Cells
• 2.3.4 Quantitative Analysis
• Determination of Relationship between Absorbance and Concentration
• Calibration Curve
• Analysis of Mixtures

• 2.4 Infrared Absorption Spectroscopy

• 2.4.1 Molecular Species That Absorb Infrared Radiation

• 2.4.2 Sample Handling Techniques
• 2.4.3 Stretching and Bending Vibrations
• 2.4.4 Qualitative Applications
• 2.4.5 Structural Analysis
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2.4 INFRARED ABSORPTION

SPECTROSCOPY
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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
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Transmittance vs Absorbance

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

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

10

microwave
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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!
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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
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Dipole moment
is a measure of the extent to which a separation exists
between the centers of positive and negative charge
within a molecule.
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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
14
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Stretching
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Bending
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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
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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
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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
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KBr Pallet Method

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Nujol Mull Method

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Interpretation of IR Spectra
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• 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)
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How to analyze IR spectra?

1.Begin by looking in the region from 4000-1300. Look at
the C–H stretching bands around 3000
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2. Look for a carbonyl in the region 1760-1690. If there is

such a band;
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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
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5. Other structural features to check for

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• 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
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Fingerprint
region
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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
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Example: decane

Peak Assignment
2800 cm-1 sp3 C-H stretching
1460 cm-1 CH2 bending
1380 cm-1 CH3 bending
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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.
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Example: cyclohexene

*Peak assignment table!

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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
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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
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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.

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

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

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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.
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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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Example: ethyl butyrate

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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
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