Infrared Spectroscopy Infrared Spectroscopy

More detailed information about

functional groups
Infrared Spectroscopy
E = h! =
hc
"
High frequencies, large wavenumbers, and
short wavelengths are associated with high
energy.
Wavenumber (!) is another way to
describe the frequency of electromagnetic
radiation absorbed.
An infrared spectrum is obtained by passing
infrared radiation through the sample
Region of infrared that is most useful lies between Region of infrared that is most useful lies between
2.5-16 2.5-16 m (4000-625 cm m (4000-625 cm
-1 -1
) )
Depends on transitions between Depends on transitions between vibrational vibrational
energy states energy states
Stretching Stretching
Bending Bending
Infrared Spectroscopy Infrared Spectroscopy
Review Review
Infrared Absorbance
Atoms/covalent bonds are in constant motion.
(Vibrate)
Each stretching and bending vibration occurs
with a distinct quantized energy
Infrared Absorbance & Molecular
Vibrations for CCl
4
Stretching & Bending
Stretching Vibrations Stretching Vibrations
Symmetric Symmetric Antisymmetric Antisymmetric
Bending Vibrations Bending Vibrations
In plane In plane In plane In plane


Bending Vibrations Bending Vibrations
Out of plane Out of plane Out of plane Out of plane



Stretching takes more energy than bending.
Bond order affects the position of absorption bands
The approximate wavenumber of an IR absorption
peakcan be calculated from Hookes law
! =
1
2#c
f(m
1
+ m
2
)
m
1
m
2
1/2
~
~
!
= the wavenumber of the stretching vibration
f = force constant
m
1
and m
2
= masses of the respective atoms
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Stretching vibrations (single bonds) Stretching vibrations (single bonds)
O O H (alcohols) H (alcohols) 3200-3600 3200-3600
O O H (carboxylic acids) H (carboxylic acids) 3000-3100 3000-3100
N N H H 3350-3500 3350-3500
Empirical Table Empirical Table
Infrared Absorption Frequencies Infrared Absorption Frequencies
2000 2000 3500 3500 3000 3000 2500 2500 1000 1000 1500 1500 500 500
Wave number, cm Wave number, cm
-1 -1
IR Spectrum of 2-Hexanol
IR Spectrum of 2- IR Spectrum of 2-Hexanol Hexanol
H H C C
O O H H
OH OH
CH CH
33
CH CH
22
CH CH
22
CH CH
22
CHCH CHCH
33
IR Spectrum of a Primary Amine (1
o
)
IR Spectrum of a Primary Amine (1 IR Spectrum of a Primary Amine (1
oo
) )
Therefore, the greater the dipole, the more intense the
absorption. (i.e., The greater the molar extinction
coefficient ($) in Beers law, A= $bc)
When a bond stretches, the increased distance
between the atoms increases the dipole moment
A bond must have a dipole or an induced dipole in order
to have a visible absorbance in the IR spectrum.
The energy (IR frequency) and intensity of the
absorption band also depends on the concentration
of the solution from Beers law, A= $bc.
Therefore, it takes less energy to stretch an OH or
N-H bond if it is hydrogen bonded.
Question Question
A) A) none none
B) B) The gas phase peak is more intense. The gas phase peak is more intense.
C) C) The gas phase peak is >4000 cm The gas phase peak is >4000 cm
-1 -1
. .
D) D) The gas phase peak is much less The gas phase peak is much less
intense. intense.
What is the difference in the O-H stretching
peak between a 1
o
alcohols liquid phase
spectrum and its spectrum in the gas
phase?
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Stretching vibrations (single bonds) Stretching vibrations (single bonds)
sp sp C C H H 3310-3320 3310-3320
sp sp
22
C C H H 3000-3100 3000-3100
sp sp
33
C C H H 2850-2950 2850-2950
sp sp
22
C C O O 1200 1200
sp sp
33
C C O O 1025-1200 1025-1200
Empirical Table Empirical Table
Infrared Absorption Frequencies Infrared Absorption Frequencies
2000 2000 3500 3500 3000 3000 2500 2500 1000 1000 1500 1500 500 500
Wave number, cm Wave number, cm
-1 -1
IR Spectrum of Hexane
IR Spectrum of Hexane IR Spectrum of Hexane
CH CH
33
CH CH
22
CH CH
22
CH CH
22
CH CH
22
CH CH
33
CCH stretching H stretching
bending bending bending bending
bending bending
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Stretching vibrations (multiple bonds) Stretching vibrations (multiple bonds)
Empirical Table Empirical Table
Infrared Absorption Frequencies Infrared Absorption Frequencies
C C C C 1620-1680 1620-1680
C C N N
C C C C 2100-2200 2100-2200
2240-2280 2240-2280
2000 2000 3500 3500 3000 3000 2500 2500 1000 1000 1500 1500 500 500
Wave number, cm Wave number, cm
-1 -1
IRSpectrum of 1-Hexene
IRSpectrum IRSpectrum of 1- of 1-Hexene Hexene
H H
22
C=CHCH C=CHCH
22
CH CH
22
CH CH
22
CH CH
33
H H C C
C=C C=C H H
C=C C=C
H H
22
C=C C=C
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Stretching vibrations (carbonyl groups) Stretching vibrations (carbonyl groups)
Aldehydes Aldehydes and and ketones ketones 1710-1750 1710-1750
Esters Esters 1730-1750 1730-1750
Amides Amides 1680-1700 1680-1700
Carboxylic acids Carboxylic acids 1700-1725 1700-1725
Acid anhydrides Acid anhydrides 1800-1850 and 1740-1790 1800-1850 and 1740-1790
Empirical Table Empirical Table
Infrared Absorption Frequencies Infrared Absorption Frequencies
C C O O
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright 2000 The McGraw-Hill Companies, Inc. All rights reserved.
2000 2000 3500 3500 3000 3000 2500 2500 1000 1000 1500 1500 500 500
Wave number, cm Wave number, cm
-1 -1
IR Spectrum of 2-Hexanone
IR Spectrum of 2- IR Spectrum of 2-Hexanone Hexanone
H H C C
C=O C=O
O O
CH CH
33
CH CH
22
CH CH
22
CH CH
22
CCH CCH
33
An atom other than carbon next to the carbonyl
group causes the position of the carbonyl absorption
band to shift
The oxygen of an ester is more electronegative.
1730-1750 cm 1730-1750 cm
-1 -1
(shorter C=O bond)
The nitrogen of an amide is less electronegative.
1680-1700 cm 1680-1700 cm
-1 -1
(longer C=O bond)
~ 1720 cm ~ 1720 cm
-1 -1
(1725-1700 cm (1725-1700 cm
-1 -1
) )
What would explain the difference in the C=O stretching
absorbances between an anhydride 1800-1850 cm 1800-1850 cm
-1 -1
and and
1740-1790 1740-1790 cm cm
-1 -1
and a carboxylic acid 1700-1725 1700-1725 cm cm
-1 -1
?
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Bending vibrations of alkenes Bending vibrations of alkenes
Empirical Table Empirical Table
Infrared Absorption Frequencies Infrared Absorption Frequencies
CH CH
22
RCH RCH
CH CH
22
R R
22
C C
CHR' CHR' cis cis-RCH -RCH
CHR' CHR' trans trans-RCH -RCH
CHR' CHR' R R
22
C C
910-990 910-990
890 890
665-730 665-730
960-980 960-980
790-840 790-840
wavenumber (cm
1
) assignment
3075
2950
1650 and 890
sp
2
CH
sp
3
CH
a terminal alkene with two substituents
Question Question
Is the following IR of cis or trans 2- Is the following IR of cis or trans 2-
pentene? pentene?
A) cis A) cis B) trans B) trans
SUMMARY:
CH bond absorption
and hybridization
of the carbon atom
Distinctive Stretch of CH Bond in an
Aldehyde (the waggle vibration)
Structural unit Structural unit Frequency, cm Frequency, cm
-1 -1
Bending vibrations of derivatives of benzene Bending vibrations of derivatives of benzene
Monosubstituted Monosubstituted 730-770 and 690-710 730-770 and 690-710
Ortho- Ortho-disubstituted disubstituted 735-770 735-770
Meta- Meta-disubstituted disubstituted 750-810 and 680-730 750-810 and 680-730
Para- Para-disubstituted disubstituted 790-840 790-840
Empirical Table Empirical Table
AROMATIC AROMATIC IR Absorption Frequencies IR Absorption Frequencies
2000 2000 3500 3500 3000 3000 2500 2500 1000 1000 1500 1500 500 500
Wave number, cm Wave number, cm
-1 -1
IR Spectrum of tert-butylbenzene
IR Spectrum of IR Spectrum of tert tert- -butylbenzene butylbenzene
H H C C
Ar Ar H H
Monsubstituted Monsubstituted
benzene benzene
C C
66
H H
55
C(CH C(CH
33
) )
33
The presence & absence of absorption bands are
must be considered in identifying a possible
structure in IR spectroscopy.
NOTE: Bonds, which lack dipole moments, are
not detected.
Analyzing Structure:
Functions & Infrared Spectra
The molecular formula is a critical piece of
information, which limits the functional possibilities.
Question Question
The following IR is most likely? The following IR is most likely?
A) A) o- o-xylene xylene
B) B) m- m-xylene xylene
C) C) p- p-xylene xylene
D) D) ethyl benzene ethyl benzene
Subtle differences can make some distinctions very difficult.
Therefore IR is used with other methods; NMR being most important.
Analyzing Infrared Spectra :
Structure & Function Questions
Question Question
The following IR is most likely? The following IR is most likely?
A) A) methylbenzamide methylbenzamide
B) B) benzoic acid benzoic acid
C) C) methylphenylketone methylphenylketone
D) D) ethyl benzene ethyl benzene
E) E) benzaldehyde benzaldehyde
Question Question
The following IR is most likely? The following IR is most likely?
A) A) propylamine propylamine
B) B) propenoic propenoic acid acid
C) C) 2- 2-propanol propanol
D) D) 2- 2-propenaldehyde propenaldehyde
E) E) 2- 2-propyne propyne-1- -1-ol ol
Question Question
The following IR is most likely? The following IR is most likely?
A) A) methylbenzamide methylbenzamide
B) B) benzoic acid benzoic acid
C) C) benzaldehyde benzaldehyde
D) D) ethylbenzylketone ethylbenzylketone
E) E) methylbenzoate methylbenzoate