Physicochemical

Analysis II
IR - Infrared Spectroscopy
A general introduction to spectroscopic methods will be
followed by a more detailed presentation on the use of IR
Spectroscopy in structural analyses of organic compounds.
Presence or absence of certain covalent bonds, especially
O-H and C=O, can be readily determined from IR spectra.
IR Spectroscopy Functional Group Determination

Molecular Dynamics
Total energy of a molecule: Etotal = Etranslation + Eelectronic + Evibration + Erotation
Etranslation = kinetic energy, 3-D movement
Eelectronic = electronic energy, excitation of electrons: ground state excited state
Evibration = vibrational energy, bending and stretching of covalent bonds
Erotation = rotational energy

Chemists can use portions of the electromagnetic spectrum (EMS)

to selectively manipulate the energies contained within a molecule,
to uncover detailed evidence of its chemical structure and bonding.

Introduction to Spectroscopy

spectrum looking

Instrumentally aided studies of the interactions between matter (sample being

analyzed) and energy (any portion of the electromagnetic spectrum, EMS)
The four most common spectroscopic methods used in organic analysis are:
Method

Abbrev.

Energy used

Units

Ultraviolet-Visible Spectroscopy
Infrared Spectroscopy

UV-Vis
IR

ultraviolet-visible
infrared

NMR

radio frequencies

nm
-1
m or cm
Hz or

Mass Spec

electron volts

amu

Nuclear Magnetic Resonance

Mass Spectroscopy

Question: What actually happens to the sample during an analysis?

{How do the sample and energy interact?}

Matter/Energy Interactions
What happens when a sample absorbs UV/Vis energy?
excitation of ground state electrons
(typically p and n electrons)
Eelectronic increases momentarily

UV/Vis
(200 nm)

p*
p p*

sample

transition

What happens when a sample absorbs IR energy?

stretching and bending of bonds
(typically covalent bonds)
Evibration increases momentarily

-O-H

IR
(3500 cm-1)

-O H

Bending & Streching

Peak & Absorption

FTIR Instrumentation
Shimadzu 8300 FTIR Spectrometer

Infrared source

Computer Workstation
running Hyper IR 1.57

sample port
(closed)

IR

Perkin-Elmer
1600 FTIR

FTIR
Sample
Port
IR

organic sample
selectively absorbs
infrared radiation

Infrared
radiation

salt plates positioned

on sample holder
calcium chloride
(CaCl2) desiccant

to detector

IR Correlation Diagram
Region I
3600-2700 cm-1

Transmittance (%)

100
80
60

O-H N-H C-H

bond stretching

C=O
Fingerprint
Region

acid chlorides
anhydrides
(below 1500 cm-1)
esters
ketones
aldehydes
carboxylic acids
amides

alcohols
phenols
carboxylic acids

40

amines
amides

20
0
4000
2.5

Region II
1800-1600 cm-1

alkynes
alkenes
alkanes

3500

3000
3.0

C-H
=C-H
-C-H

2500
4.0

2000
5.0

1500
6.0

Frequency (cm-1) / Wavelength (microns, m)

1000
10.0

IR Correlation Diagram

Transmittance (%)

100

80
60

Region I
3600-2700 cm-1

Region II
1800-1600 cm-1

O-H N-H C-H

bond stretching

C=O
acid chlorides
anhydrides
(below 1500 cm-1)
esters
ketones
aldehydes
carboxylic acids
amides

alcohols
phenols
carboxylic acids

40

amines
amides

20
0
4000

Fingerprint
Region

alkynes
alkenes
alkanes

3500

3000

C-H
=C-H
-C-H

O=C=O
CN
CC

2500

Frequency (cm-1)

2000

C=N
C=C

1500

C-F

1000