Previously on Eldas

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Spectroscopy

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Spectroscopy
High Frequency () Low
High Energy (E) Low
Short Wavelength () Long

1019 Hz 1015 Hz 1013 Hz

4000 cm-1 0.01 cm-1
1 x108 cm-1 400 cm-1 10 cm-1 3 cm-1 0.002 cm-1

Cosmic
Vacuum
& X-Ray Infrared Microwave Radio Frequency
UV
 Ray

0.1 nm 190 nm 1 mm 30 cm
Near Visible Vibrational Nuclear
Ultraviolet Infrared Magnetic
Resonance
200 nm 400 nm 800 nm 2.5  15 
1m 5m
Blue Red
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Spectroscopy

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Spectroscopy
Spectroscopy Types:
▪ Infrared Spectroscopy (IR)
Vibrational Energy States - Functional Groups
▪ Nuclear Magnetic Resonance Spectroscopy (NMR)
Spin States - The number, type, and relative position of hydrogen atoms
(protons) and carbon atoms
▪ Mass Spectrometry (MS)
Hi-Energy Electron Bombardment - Molecular Weight
▪ Ultraviolet Spectroscopy (UV)
Electronic Energy States - Electronic structure of unsaturated molecules and
measurement of extent of conjugation

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Infra Red Spectrophotometer

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Hooke’s Law

1715 vs 1675 cm-1

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FTIR Applications
• Qualitative Analysis
• Degree of unsaturation of fatty acids
• Degree of deacetylation of chitosans
• Adsorption mechanism predictions
• etc

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General Interpretation

• Shape
• Intensity

Peak intensity is dependent on amount of sample and sensitivity of instrument; therefore, the actual
intensity can vary from spectrum to spectrum 11
Characterization of Functional Groups

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 C-H Stretch 3000–2840 cm-1
Alkanes CH2 bending 1465 cm-1
CH3 bending 1375 cm-1

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 =C-H Stretch 3095–3010 cm-1.
Alkenes =C-H bending 1000–650 cm-1
C=C Stretch 1660–1600 cm-1; conjugation moves C=C
stretch to lower frequencies and increases the
intensity.

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 Symmetrically disubstituted (trans) double
Alkenes bonds are often vanishingly weak in
absorption; cis are stronger

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Cyclohexane or
Cyclohexene?

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Nitriles

C≡C stretching 2250 cm-1 (sharp) 18

Aromatics

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Alcohols
• The free O-H stretch sharp peak at 3650–3600 cm-1
• The hydrogen-bonded O-H broad peak at 3400–3300 cm-1

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Alcohols
• C-O-H Bending broad and weak at 1440 –1220 cm-1
• C-O Stretching 1260–1000 cm-1. This band can be used to assign a
primary, secondary, or tertiary structure to an alcohol.

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Ethers • C-O-C stretching at 1300 –1100 cm-1.

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Carbonyl Compounds
• Strong, sharp C=O peak 1650 to 1850 cm−1
• Exact absorption characteristic of type of carbonyl compound depend
on: inductive effect, resonance and hydrogen bond formation.

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Aldehydes

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Aldehydes

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Ketones

• C=O bending medium

peak at 1100-1300 cm-1
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Carboxylic Acids
• O-H stretch, very broad, 3400-2400 cm-1. Often overlap with C-H
bond absorption.
• C=O stretch, broad, 1730-1700 cm-1.
• C-O stretch, medium, 1320-1210 cm-1.

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Esters

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Amides
• N-H stretch, primary amides, 3350 and 3180 cm-1. Secondary amides,
3000 cm-1.
• C=O stretch, 1700-1640 cm-1.
• N-H bending, primary and secondary amides, 1640-1550 cm-1.

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Acid Chlorides
• C=O stretch, 1810-1775 cm-1. Conjugated, 1780-1760 cm-1
• C-Cl stretch, 730-550 cm-1.

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Acid Anhydrides
• C=O stretch, 1830-1800 cm-1 and 1775-1740 cm-1 .
• C-O stretch, 1300-900 cm-1.

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 Amines
• N-H stretch, 3500-3300 cm-1.
• Primary: two bands;
• Secondary: one band, weak for
aliphatic and stronger for
aromatic;
• tertiary: no band.
• C=O stretch, 1700-1640 cm-1.
• N-H bending,
• primary: 1640-1560 cm-1
• secondary 1500 cm-1.
• N-H oop 800 cm-1.
• C-N stretch, 1350-1000 cm-1.
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Nitro
• Alyphatic nitro assym. stretch, strong,
1600-1530 cm-1 and symm. Strecth,
medium, 1390-1300 cm-1 .
• Alyphatic nitro assym. stretch, strong,
1550-1490 cm-1 and symm. Strecth,
strong, 1355-1315 cm-1 .

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Alkyl halides

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Alkyl halides

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 Analyzing the Spectrum – A Suggested Approach
Step 1. – Check for the presence of the Carbonyl group (C=O) at
1715 cm-1. If molecule is conjugated, the strong (C=O)
absorption will be shifted to the right by ~30 cm-1,
i.e. ~1685 cm-1
If the carbonyl absorption is present, check for:
▪ Carboxylic Acids - Check for OH group (broad absorption
near 3300-2500 cm-1)
▪ Amides - Check for NH group
(1 or 2 absorptions near 3500 cm-1)
▪ Esters - Check for C-O group (medium
absorptions near 1300-1000 cm-1)
▪ Anhydrides - Check for 2 C=O absorptions near
1810 and 1760 cm-1
▪ Aldehydes - Check for Aldehyde CH group (2 weak
absorptions near 2850 and 2750 cm-1)
▪ Ketones - Ketones (The above groups have been
eliminated)
Step 2. - If the Carbonyl Group is Absent Check for Alcohols,
Amines, or Ethers.
▪ Alcohols & Phenols - Check for OH group (Broad
absorption near 3600-3300 cm-1
Confirm present of C−O near
1300-1000 cm-1
▪ Amines - Check for NH stretch (Medium
absorptions) near 3500 cm-1
Primary Amine - 2 Peaks
Secondary Amine - 1 Peak
Tertiary Amine - No peaks
N-H scissoring at 1560 - 1640 cm-1
▪ Ethers - Check for C-O group near 1300-
1000 cm-1 and absence of OH
Step 3. – Refine the Structure Possibilities by Looking for
Double Bonds, Triple Bonds and Nitro Groups
▪ Double Bonds - C=C is weak absorption near 1650 cm-1
Aliphatics occur on right side of
3000 cm-1.
Unsaturated C=C or CC bonds show
an absorption on the left side of 3000
cm-1.
▪ Triple Bonds - CN (medium, sharp absorption near
2250 cm-1
CC (weak, sharp absorption near
2150 cm-1
▪ Nitro Groups - Two strong absorptions 1600-1500 cm-1
and 1390-1300 cm-1
Step 3 (Con’t)
Aromatic Ring Absorptions
▪ Aromatic unsaturated C=C bonds show an absorption
on the left side of 3000 cm-1, but the aromaticity must
be verified in the overtone region (1667 - 2000cm-1) and
the out-of-plane (OOP) region (900 - 690 cm-1)
▪ Medium to strong absorption in region 1650 - 1450 cm-1
▪ Many weak combination and overtone absorptions
appear between 2000 and 1667 cm-1
The relative shapes and numbers (1 - 4) of the overtone
absorptions can be used to tell whether the aromatic
ring is monosubstituted or di-, tri-, tetra-, penta-, or
hexasubstituted.
Positional (ortho-, meta-, para-) isomers can also be
distinguished.
Note: A strong carbonyl absorption can overlap these
ovetone bands, making them unusable.
Step 3 (Con’t)
Aromatic Ring Absorptions (Con’t)
▪ The unsaturated =C-H “Out-of-Plane (OOP) bending
absorptions in the region 900 – 690 can also be used
to determine the type of ring substitution.
▪ The number of absorptions and their relative positions
are unique to each type of substitution.
▪ Although these absorptions are in the “fingerprint”
region they are particularly reliable for rings with alkyl
group substitutions.
▪ They are less reliable for polar substituents.
Step 4. If none of the above apply then the compound is
most likely a hydrocarbon.

Generally, very simple spectrum

Hydrocarbons - Check for main absorptions near

right side of 3000 cm-1
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Let’s reveal
the mystery

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C6H14

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C7H6O3

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SDBS • https://sdbs.db.aist.go.jp/sdbs/cgi-bin/ENTRANCE.cgi

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To Be Continued

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