1.IR Spectroscopy EDITED
1.IR Spectroscopy EDITED
1.IR Spectroscopy EDITED
IR Spectroscopy
1
Electromagnetic radiation
The spectrum covers EMA wave energy having wavelengths from
thousands of meters down to fractions of the size of an atom.
Frequencies of 30 Hz and below can be produced by and are
important in the study of certain stellar nebulae and frequencies as
high as 2.9×1027 Hz have been detected from astrophysical sources.
Electromagnetic energy at a particular wavelength λ (in vacuum) has
an associated frequency (ʋ) and photon energy E. Thus, the
electromagnetic spectrum may be expressed equally well in terms of
any of these three quantities. They are related by the equations:
E= hʋ = hc/λ
Energy of electromagnetic waves
1
c
c
E h h hc
c
E N A h N A h N A hc
(nu-bar) represents wavenumber, the
number of wavelengths in 1 cm
Electromagnetic
Electromagnetic Spectrum
Spectrum
13
IR radiation sources
1.Nernst glower
2.Incandescent lamp
3.Mercury arc
4.Tungsten lamp
5.Globar source
6.Nichrome wire
15
Sample cells and sampling of substances
17
Infrared Spectroscopy of
Organic Molecules
• IR region lower energy than visible light (below red –
produces heating as with a heat lamp)
Introduction
The IR Spectroscopic Process
There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond
H H
C
C
H
H
symmetric asymmetric
H H
C H H
C
C C
H H
H H
➢Polar
➢No center of symmetry of vibration causing absorption
➢Change in dipole moment on undergoing vibration
H H3C H3C
H3C ClH2C ClH2C
C O C O C O C O C O C O
O C H
Hydrogen Bonding:
In organic compounds like phenols, acids or amines which show hydrogen
bonding, the value of force constant generally decreases because of attraction
and this shifts absorption towards lower wave number.
•Intermolecular H-bonding gives broader bands while intramolecular H-
bonding gives sharp and well defined bands.
•The absorption bands in intermolecular H-bonding are concentration
dependent but not in case of intramolecular H-bonding. Why?
The IR Spectroscopic Process
As a covalent bond oscillates – due to the oscillation of the dipole of
the molecule – a varying electromagnetic field is produced
The greater the dipole moment change through the vibration, the
more intense the EM field that is generated
The IR Spectroscopic Process
When a wave of infrared light encounters this oscillating EM field generated
by the oscillating dipole of the same frequency, the two waves couple, and
IR light is absorbed
“coupled” wave
EM oscillating wave
from bond vibration
D. The IR Spectrum
1. Each stretching and bending vibration occurs with a characteristic
frequency as the atoms and charges involved are different for different
bonds
D. The IR Spectrum
2. The x-axis of the IR spectrum is in units of wavenumbers, n, which is the
number of waves per centimeter in units of cm-1 (Remember E = hn or E =
hc/l)
D. The IR Spectrum
3. This unit is used rather than wavelength (microns) because
wavenumbers are directly proportional to the energy of transition
being observed – chemists like this, physicists hate it
4. This unit is used rather than frequency as the numbers are more
“real” than the exponential units of frequency
6. In general:
Lighter atoms will allow the oscillation to be faster – higher energy
This is especially true of bonds to hydrogen – C-H, N-H and O-H
Fingerprint
Region
4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 600 cm-1
Infrared Spectroscopy
Octane
1. Alkanes – combination of C-C and C-H bonds H
• C-C stretches and bends 1360-1470 cm-1
H C
H
• CH2-CH2 bending 1450-1470 cm-1 (m)
(w – s) (m)
Infrared Spectroscopy 1-Octene
2. Alkenes – addition of the C=C and vinyl C-H bonds
H
• C=C stretch at 1620-1680 cm-1 weaker as C
H C
substitution increases
H
• vinyl C-H stretch occurs at 3000-3100 cm-1
(w – m)
(w – m)
Infrared Spectroscopy
1-Octyne
3. Alkynes – addition of the C=C and vinyl C-H bonds
• C≡C stretch 2100-2260 cm-1; strength depends on
asymmetry of bond, strongest for terminal alkynes, H C C
weakest for symmetrical internal alkynes
(w-m)
(m – s)
Infrared Spectroscopy
Ethyl benzene
4. Aromatics H
• Due to the delocalization of e- in the ring, C-C bond
order is 1.5, the stretching frequency for these
bonds is slightly lower in energy than normal C=C
• These show up as a pair of sharp bands, 1500 &
1600 cm-1, (lower frequency band , s)
(w – m) (w – m)
Infrared Spectroscopy
4. Aromatics
• If the region between 1667-2000 cm-1 (w) is free of interference (C=O stretching
frequency is in this region) a weak grouping of peaks is observed for aromatic
systems
• Analysis of this region, called the overtone of bending region, can lead to a
determination of the substitution pattern on the aromatic ring
Monosubstituted
G
G
1,2 disubstituted (ortho or o-)
G
1,2 disubstituted (meta or m-)
G
G
1,4 disubstituted (para or p-)
G
IR spectra BENZENEs
=C—H bond, “unsaturated” “aryl”
(sp2) 3000-3100 cm-1
+ 690-840
mono-substituted + 690-710, 730-770
ortho-disubstituted + 735-770
meta-disubstituted + 690-710, 750-810(m)
para-disubstituted + 810-840(m)
R H
C C 960-980 R 735-770
H R
R
R R
C C 665-730 860-900
H H R 750-810
680-725
R
R
C CH2 885-895
R
R R 800-860
R R
C C 790-840
R H
Infrared Spectroscopy
Diisopropyl ether
6. Ethers – addition of the C-O-C asymmetric band and
vinyl C-H bonds
• Show a strong band for the antisymmetric C-O-C
stretch at 1050-1150 cm-1 O
• Otherwise, dominated by the hydrocarbon
component of the rest of the molecule
(s)
Infrared Spectroscopy
1-butanol
7. Alcohols
• Strong, broad O-H stretch from 3200-3400 cm-1 H
O
• Like ethers, C-O stretch from 1050-1260 cm -1
(m– s)
br
(s)
IR spectra ALCOHOLS & ETHERS
(w) (w)
Infrared Spectroscopy
pyrrolidine
9. Amines – Secondary
• N-H band for R2N-H occurs at 3200-3500 cm-1
as a single sharp peak weaker than –O-H N H
• Tertiary amines (R3N) have no N-H bond and
will not have a band in this region
(w – m)
Infrared Spectroscopy
• Peaks from 2850-3000 are simply sp3 C-H in most organic molecules
V-shape peak
-N—H bond for 2o
Broad U-shape peak amine (R2N—H)
-O—H bond
W-shape peak
-N—H bond for 1o
amine (RNH2)
Sharp spike 3000 cm-1
-C≡C—H bond
Small peak shouldered
just above 3000 cm-1
C=C—H or Ph—H
Infrared Spectroscopy
Cyclohexyl carboxaldehyde
10. Aldehydes O
• C=O (carbonyl) stretch from 1720-1740 cm-1 C
H
• Band is sensitive to conjugation, as are all
carbonyls (upcoming slide)
(w-m)
(s)
Infrared Spectroscopy
3-methyl-2-pentanone
11. Ketones O
• Simplest of the carbonyl compounds as far as IR
spectrum – carbonyl only
(s)
IR: Carbonyl Compounds
• Strong, sharp C=O peak 1670 to 1780 cm1
• Exact absorption characteristic of type of carbonyl
compound
– 1730 cm1 in saturated aldehydes
– 1705 cm1 in aldehydes next to double bond or
aromatic ring
Infrared Spectroscopy
Ethyl pivalate
12. Esters O
• C=O stretch at 1735-1750 cm-1
O
• Strong band for C-O at a higher frequency than
ethers or alcohols at 1150-1250 cm-1
(s)
(s)
Infrared Spectroscopy
4-phenylbutyric acid
13. Carboxylic Acids:
• Gives the messiest of IR spectra O
C H
• C=O band occurs between 1700-1725 cm -1 O
• The highly dissociated O-H bond has a broad band from 2400-
3500 cm-1 covering up to half the IR spectrum in some cases
(w – m) (s) (s)
br
Infrared Spectroscopy
Propionic anhydride
14. Acid anhydrides O O
(s) (s)
Infrared Spectroscopy
Propionyl chloride
O
15. Acid halides
• Clefted band at 1770-1820 cm-1 for C=O
Cl
• Bonds to halogens, due to their size (see Hooke’s
Law derivation) occur at low frequencies, only Cl is
light enough to have a band on IR, C-Cl is at 600-
800 cm-1
(s)
(s)
Infrared Spectroscopy
pivalamide
O
16. Amides
• Display features of amines and carbonyl compounds
• C=O stretch at 1640-1680 cm-1 NH2
(m – s) (s)
Infrared Spectroscopy
2-nitropropane
17. Nitro group (-NO2) O
O
(s) (s)
Infrared Spectroscopy
propionitrile
18. Nitriles (the cyano- or –C≡N group) N
• Principle group is the carbon nitrogen triple C
bond at 2100-2280 cm-1
(s)
Infrared Spectroscopy
Effects on IR bands
1. Conjugation – by resonance, conjugation lowers the
energy of a double or triple bond. The effect of this is
readily observed in the IR spectrum:O
O
O O
O
N C
H 2N C CH 3 vs.
CH3
O
Effects on IR bands
1. Steric effects – usually not important in IR spectroscopy, unless they reduce the
strength of a bond (usually p) by interfering with proper orbital overlap:
O O
CH 3
C=O: 1686 cm-1 C=O: 1693 cm-1
• Here the methyl group in the structure at the right causes the carbonyl
group to be slightly out of plane, interfering with resonance
2. Strain effects – changes in bond angle forced by the constraints of a ring will
cause a slight change in hybridization, and therefore, bond strength
O O O
O O
1815 cm-1 1775 cm-1 1750 cm-1 1715 cm-1 1705 cm-1
Effects on IR bands
1. Hydrogen bonding
• Hydrogen bonding causes a broadening in the
band due to the creation of a continuum of bond
energies associated with it
• In the solution phase these effects are readily
apparent; in the gas phase where these effects
disappear or in lieu of steric effects, the band
appears as sharp as all other IR bands:
OH
Gas phase spectrum of
1-butanol
H
O O
Steric hindrance to H-bonding
in a di-tert-butylphenol C=O; 1701 cm-1
NOW WE WILL
MOVE FORWARD
TO SOME
QUESTIONS
Which compound is this?
a) 2-pentanone 1-pentanol
b) 1-pentanol
c) 1-bromopentane
d) 2-methylpentane
What is the compound?
a) 1-bromopentane 2-pentanone
b) 1-pentanol
c) 2-pentanone
d) 2-methylpentane
C8H6
phenylacetylene
C4H8
Unst’d
1640- 880-
1680
900
C=C
R2C=CH2
isobutylene CH3
CH3C=CH2
tert-butyl alcohol
O-H
C-O 3o
2-butanone
C=O
~1700 (s)
APPLICATIONS OF IR SPECTROSCOPY TO BIOMOLECULES
APPLICATIONS OF IR SPECTROSCOPY TO NATURAL
PRODUCTS/EXTRACTS
Nicotine
3400cm-1 = water, 2970, 2780 cm-1 =CH stretching , 1677 cm-1 = aromatic C=N,
1691 cm-1 = C=Cstrecting , 717 cm-1 and 904 cm-1 out of plane bending of the
C-H bond of pyridine ring
In this spectrum, we can notice several peaks, which
characterize the different chemical functions of
Nicotine:
• Around 3400 cm-1 , we can see the large peak of
water (it deals with a liquid film).
• Between 2970 and 2780 cm-1: C-H stretching.
• The peak at 1677 cm-1 : aromatic C=N double
bond stretching.
• The peak at 1691 cm-1 : aromatic C=C double
bond stretching.
• The peaks at 717 cm-1 and 904 cm-1 correspond to
the out of plane bending of the C-H bond of the
monosubstituted pyridinic cycle.
Research Work
Re-Sn Schiff base complex
N
N
O
O
NH
NH
N
N toluene,
R 2SnO
6 h
O
HO
R=C6H5 DPTC (2a)
Sn O R=CH3 DMTC (2b)
R
HO
R=C8H17 DOTC (2c)
Schif f base (1) R
CO
toluene,
16 h, -2CO
OC CO
Re +
OC CO
Br
CO
OC O
Re
OC NH
N
Br
O
R=C6H5 ReDPTC (3)
Sn
R=CH3 ReDMTC (4)
R O
R=C8H17 ReDOTC (5)
R
H
O N
FTIR spectra of Schiff base (1) N
HO
OH
70 N
60
50
Transmittance
40
30
20 3360
2826
10
2968
3390 1618
0
1677
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
H
O N
N
FTIR spectra of Sn Schiff base complex (2a)
O
60 Sn O
N
50
40
30
20
10 735
1558
3427 1366 676
1603
0 1447
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
N
CO
FTIR spectra of Re-Sn Schiff base complex (3) OC O
Re
OC NH
N
Br
80
70
O
60
Sn O
Ph
50
742
Ph
1195 691
2923 1350
%T
40
30 1610 1454
3442
1566
20
1951 1506
10 2032
1929
0
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
Schiff base coated Fe3O4 nanoparticles
70
Transmittance
60
1632
631
50 1506 580
1543
40 1588
1440
30
1647
20 3412
639 572
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
3412, 1647 cm-1 for absorbed water on surface of Fe3O4 nanoparticles.
639, 572 cm-1 for Fe-O strecthing. Presence of additional peaks in the spectra
of Fe3O4@Schiff base, majorly corresponding to C=O, C=N and C-C in the region
1500-1632 cm-1
END