Infrared Analysis Spectroscopic: The Electromagnetic Spectrum The Electromagnetic Spectrum

Infrared
Spectroscopic
Analysis
The Electromagnetic Spectrum
Gamma
Radio waves Mcrowaves Infared Visible UV X rays
rays
Decreasing wavelength
Increasing frequency
Increasing energy
ARMSALCEDO alanx3@yahoo.com
1
The Infrared
800nm – 2500nm
2.5 µm 25 µm
Spectroscopy
study of spectra
study of the quantized interaction of energy (electromagnetic

radiation) with matter
the basis of spectroscopy is that each chemical element has its

own characteristic spectrum
“In Organic Chemistry, we deal with molecular spectroscopy.”
2
Spectroscopic Techniques
Visible
γ - rays X - rays UV Infrared Microwaves Radio Waves Long Radio
Waves
FM AM
Nuclear
transformations
Core electron Molecular vibrations Nuclear spin flips

excitations
Electronic Molecular rotations
excitations
Spectroscopic Techniques
Application in Structure Elucidation

Spectroscopic Techniques Information deduced
Presence of conjugated
UV-VIS
multiple bonds
Infrared Detection of functional groups
Detection and quantity of
Nuclear magnetic resonance
hydrogen and carbon atoms
Determination of molecular
Mass spectrometry mass and deduction of
molecular structures
3
Theory of Infrared Spectroscopy
molecules vibrate at specific frequencies corresponding to their

energy levels
when a molecule absorbs IR radiation, the amplitude of vibration

increases
knowing that each frequency corresponds to a certain molecular

motion, one can determine what kinds of molecular motions are
present
the kinds of bonds (functional groups) can be determined

through interpretation of these motions
Units in Infrared Spectroscopy
WAVELENGTH, λ
nanometer (nm) = 10-9
micrometer (µm) = 10-6
WAVENUMBER, ν 1
ν (in cm-1) = x 104
wavelength in µm
TRANSMITTANCE
Iout
%T= x 100
Iin
4
IR Spectrum
plot of wave number vs % transmittance
2.5 Micrometers 16
Transmittance (%)
Diagnostic region Fingerprint region
4000 3000 2000 1500 1200 1000 800 666

Wave number (cm-1)
IR Spectrum
2.5 Micrometers 16
Transmittance (%)
N H C O
C C Other stretchings,
O H C C bendings and
C N combination bands
C H C N
stretchings
4000 3000 2000 1500 1000 800 666

Wave number (cm-1)
5
IR Spectrum
Intensities of absorption bands
Strong (s)
Medium (m)
Weak (w)
Variable (v)
IR Spectrum
Shapes of absorption bands
Broad
Sharp
Multiplet
6
IR Correlation Table
IR Spectra Analysis
Carbon-Carbon Bond Stretching
• Stronger bonds absorb at higher frequencies:

– C-C 1200 cm-1
– C=C 1660 cm-1
– C≡C 2200 cm-1 (weak or absent if internal)
• Conjugation lowers the frequency:
– isolated C=C 1640-1680 cm-1
– conjugated C=C 1620-1640 cm-1
– aromatic C=C approx. 1600 cm-1
7
IR Spectra Analysis
Carbon-Hydrogen Stretching
Bonds with more s character absorb at a higher
frequency.
– sp3 C-H, just below 3000 cm-1 (to the right)
– sp2 C-H, just above 3000 cm-1 (to the left)
– sp C-H, at 3300 cm-1
IR Spectra Analysis
8
IR Spectra Analysis
IR Spectra Analysis
9
IR Spectra Analysis
O-H and N-H Stretching
• Both of these occur around 3300 cm-1, but they look

different.
– Alcohol O-H, broad with rounded tip.
– Secondary amine (R2NH), broad with one sharp spike.
– Primary amine (RNH2), broad with two sharp spikes.
– No signal for a tertiary amine (R3N) =>
IR Spectra Analysis
10
IR Spectra Analysis
IR Spectra Analysis
Carbonyl Stretching
• The C=O bond of simple ketones, aldehydes, and
carboxylic acids absorb around 1710 cm-1.
• Usually, it’s the strongest IR signal.
• Carboxylic acids will have O-H also.
• Aldehydes have two C-H signals around 2700 and
2800 cm-1.
11
IR Spectra Analysis
IR Spectra Analysis
12
IR Spectra Analysis
O-H Stretch of a Carboxylic Acid

This O-H absorbs broadly, 2500-3500 cm-1, due to strong hydrogen bonding.
IR Spectra Analysis
Variations in C=O Absorption
• Conjugation of C=O with C=C lowers the stretching frequency to

~1680 cm-1.
• The C=O group of an amide absorbs at an even lower frequency,
1640-1680 cm-1.
• The C=O of an ester absorbs at a higher frequency, ~1730-1740 cm-1.
• Carbonyl groups in small rings (5 C’s or less) absorb at an even higher
frequency.
13
IR Spectra Analysis
IR Spectra Analysis
Carbon - Nitrogen Stretching
• C - N absorbs around 1200 cm-1.

• C = N absorbs around 1660 cm-1 and is much stronger than the
C = C absorption in the same region.
• C ≡ N absorbs strongly just above 2200 cm-1. The alkyne C ≡ C
signal is much weaker and is just below 2200 cm-1 .
14
IR Spectra Analysis
Comparison
of
IR Spectra
15
Hexane
1-Hexene
1-Hexene
1-Hexyne
16
Cyclohexane
Cyclohexene
Ethanol
Phenol
17
Acetic Acid
Benzoic Acid
Benzene
Toluene
18
Ethyl Acetate
Ethylamine
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19
Molecular Modes of Vibration
Symmetric stretching Scissoring Rocking
Asymmetric stretching Wagging Twisting
Stretching vibrations Bending vibrations
Transmittance
SAMPLE
Incident IR (Iin) Transmitted IR (Iout)
100% T = no light absorbed by the sample
0% T = all light absorbed by the sample
20

Infrared Analysis Spectroscopic: The Electromagnetic Spectrum The Electromagnetic Spectrum

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Infrared Analysis Spectroscopic: The Electromagnetic Spectrum The Electromagnetic Spectrum

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Copyright:

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Infrared

The Electromagnetic Spectrum

study of the quantized interaction of energy (electromagnetic

the basis of spectroscopy is that each chemical element has its

“In Organic Chemistry, we deal with molecular spectroscopy.”

Core electron Molecular vibrations Nuclear spin flips

Application in Structure Elucidation

molecules vibrate at specific frequencies corresponding to their

when a molecule absorbs IR radiation, the amplitude of vibration

knowing that each frequency corresponds to a certain molecular

the kinds of bonds (functional groups) can be determined

Units in Infrared Spectroscopy

Diagnostic region Fingerprint region

4000 3000 2000 1500 1200 1000 800 666

4000 3000 2000 1500 1000 800 666

Intensities of absorption bands

Shapes of absorption bands

Carbon-Carbon Bond Stretching

• Stronger bonds absorb at higher frequencies:

O-H and N-H Stretching

• Both of these occur around 3300 cm-1, but they look

O-H Stretch of a Carboxylic Acid

Variations in C=O Absorption

• Conjugation of C=O with C=C lowers the stretching frequency to

Carbon - Nitrogen Stretching

• C - N absorbs around 1200 cm-1.

Symmetric stretching Scissoring Rocking

Asymmetric stretching Wagging Twisting

Stretching vibrations Bending vibrations

Incident IR (Iin) Transmitted IR (Iout)

100% T = no light absorbed by the sample

0% T = all light absorbed by the sample

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