Infrared Spectroscopy

Absorption of IR light in different

regions is characteristic of the
various functional groups present

Electromagnetic Radiation Spectrum

E =hn
ln = c

Molecular Excitation
electronic
|
vibrational

Infrared Spectrometer
(double-beam)

I0

Detector Types
diode array
Fourier Transfer
Ours is FT single beam

Perkin Elmer FTIR

IR Sample Types and Holders

Solid (KBr pellet)

or
powder w/ ATR*

*ATR = attenuated total

reflectance apparatus

Liquid (neat / pure)

Solution

Gas

Basic frequency (n)

and wavelength (l)
relationships
E = hn
n=c/l

Typical IR spectrum

% Transmittance = (I/I0)(100)
Absorbance (A) = log(I0/I)

wavelength (l)

~ frequency (n)

2.5m

15m
wavenumbers (Kaysers) cm-1

_
n = 104/l (microns)

m = 10-6 m
cm = 10-2 m

Typical IR spectrum
1500

Diagnostic Region Fingerprint Region

2.5m

15m

Isomer IR Spectra
similar, but different

Uses of IR Spectra
1. Identity - by exact spectral match
2. Purity - by band resolution & additional peaks
3. Concentration Absorbance + Std. curves

4. Structure Analysis by characteristic bands

"Back of the Envelop" Regions

3600 3200

OH, NH stretch

nOH, NH

3300 3000

CH unsat'd stretch

nCH unsat

3000 2700

CH sat'd stretch

nCH sat

2300 2100

triple bonds

nCN, CC

1800 1650

C=O stretch

nC=O

1700 1600

C=C stretch

nC=C

1600 1500

aromatic C-H bend

dCH arom

Carbonyl (C=O) Details

1740 cm-1
ester

1720 cm-1
aldehyde
ketone
carboxylic acid

conjugation effects

1680 cm-1
amide

Colthup Chart 1

Colthup Chart 2

Key Spectral Features of

Major Functional Groups

Alkane

|nCH satd (below 3000 cm-1)

Alkene
nCH unsatd |

(above 3000 cm-1)

| nC=C

**
*
*
**

(1600-1700 cm-1)

Aromatic
*

4 regions (cm-1) *
> 3000
1600-2000
1500-1600
700-850

in plane

out of plane

Aromatic Substitution Patterns

Ethers, Alcohols
1000-1200 nC-O-C

3200-3600 nO-H
strong, broad, symmetrical

hard to identify

easy to identify

Phenols
Aromatic +
OH strong, broad, symmetrical

Note: the nOH region

appears broad, butsimply
due to scale of X-axis

Ketones
ca 1720 nC=O

note C=O shift ->

due to conj'n

Aldehydes & Carboxlic Acids

ca 1720
nC=O

nC=O
ca 1720
&
nO-H
2700 3600
v. strong & broad

Esters

ca. 1740 nC=O

ca 1780
<- conj. to
ester C-O-C

Carbonyl (C=O) Details

1740 cm-1
ester

1720 cm-1
aldehyde
ketone
carboxylic acid

conjugation effects

1680 cm-1
amide

3200-3600
(weaker than OH)

nN-H

Amine

Amine classes

Amide
ca 1680
nC=O

Problem Assignment

Spectrum Interpretation label peaks

3600 3200

OH, NH stretch

nOH, NH

3300 3000

CH unsat'd stretch

nCH unsat

3000 2700

CH sat'd stretch

nCH sat

2300 2100

triple bonds

nCN,CC

1800 1650

C=O stretch

nC=O

1700 1600

C=C stretch

nC=C

1600 1500

aromatic C-H bend

dCH arom

Lab Assignment

Spectrum Interpretation label peaks

3600 3200

OH, NH stretch

nOH, NH

3300 3000

CH unsat'd stretch

nCH unsat

3000 2700

CH sat'd stretch

nCH sat

2300 2100

triple bonds

nCN,CC

1800 1650

C=O stretch

nC=O

1700 1600

C=C stretch

nC=C

1600 1500

aromatic C-H bend

dCH arom

Spectra for Problems

Spectrum Interpretation label peaks

3600 3200

OH, NH stretch

nOH, NH

3300 3000

CH unsat'd stretch

nCH unsat

3000 2700

CH sat'd stretch

nCH sat

2300 2100

triple bonds

nCN,CC

1800 1650

C=O stretch

nC=O

1700 1600

C=C stretch

nC=C

1600 1500

aromatic C-H bend

dCH arom

Anhydride, Acid chloride

Nitrile & Nitro

Amino Acid

C-Cl bond