SPECTROSCOPY 3.

3.1 INFRARED ABSORPTION SPECTROSCOPY

Infrared (IR) absorption spectroscopy is a common technique that is used to identify the major
functional groups in a compound. The identification of these groups depends upon the amount of
infrared radiation absorbed and the particular frequency (measured in cm−1, wave-numbers) at
which these groups absorb. Thus, infrared absorption spectroscopy is the measurement of the wave-
length and intensity of the absorption of mid-infrared light by a sample. Mid-infrared light (2.5 – 50 mm,
4000 – 200 cm−1) is energetic enough to excite molecular vibrations to higher energy levels. The
wavelength of many infrared absorption bands are characteristic of specific types of chemical bonds,
and infrared spectroscopy finds its greatest utility for qualitative analysis of organic and
organometallic molecules. Infrared spectroscopy is used to confirm the identity of a particular com-
pound and as a tool to help determine the structure of a molecule.
Significant for the identification of the source of an absorption band are intensity (weak, medium
or strong), shape (broad or sharp), and position (cm−1) in the spectrum. Characteristic examples are
provided in the table below to assist the user in becoming familiar with the intensity and shape
absorption bands for representative absorptions.

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen

Abbreviations Used in the Table

m, moderately strong var, of variable strength
m–s, moderate to strong w, weak
s, strong w–m, weak to moderately strong

(Continued)
3.4 SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

Alkane residues attached to carbon (continued)
 SPECTROSCOPY 3.5

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

Alkane residues attached to miscellaneous atoms (continued)

(Continued)
3.6 SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

Alkane residues attached to miscellaneous atoms (continued)
 SPECTROSCOPY 3.7

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

(Hydroxyl group O[H compounds) (Continued)

(Continued)
3.8 SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

Amine, imine, ammonium, and amide N[H
 SPECTROSCOPY 3.9

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued)

Group Band, cm−1 Remarks

Amine, imine, ammonium, and Miscellaneous R[H

TABLE 3.2 Absorption Frequencies of Triple Bonds

Abbreviations Used in the Table

m, moderately strong var, of variable strength
m–s, moderate to strong w–m, weak to moderately strong
s, strong

(Continued)
3.10 SECTION THREE

TABLE 3.2 Absorption Frequencies of Triple Bonds (Continued)

Group Band, cm−1 Remarks

*Conjugation with olefinic or acetylenic groups lowers the frequency and raises the intensity. Conjugation with carbonyl
groups usually has little effect on the position of absorption.

TABLE 3.3 Absorption Frequencies of Cumulated Double Bonds

Abbreviations Used in the Table

m–s, moderate to strong vs, very strong
s, strong w, weak
 SPECTROSCOPY 3.11

TABLE 3.3 Absorption Frequencies of Cumulated Double Bonds (Continued)

Group Band, cm−1 Remarks

3.1.1 Intensities of Carbonyl Bands

Acids generally absorb more strongly than esters, and esters more strongly than ketones or aldehydes.
Amide absorption is usually similar in intensity to that of ketones but is subject to much greaer
variations.
3.12 SECTION THREE

3.1.2 Position of Carbonyl Absorption

The general trends of structural variation on the position of C˙O stretching frequencies may be
summarized as follows:
1. The more electronegative the group X in the system R[CO[X[, the higher is the frequency.
2. a, b Unsaturation causes a lowering of frequency of 15 to 40 cm−1, except in amides, where little
shift is observed and that usually to higher frequency.
3. Further conjugation has relatively little effect.
4. Ring strain in cyclic compounds causes a relatively large shift to higher frequency. This phe-
nomenon provides a remarkably reliable test of ring size, distinguishing clearly between four-,
five-, and larger-membered-ring ketones, lactones, and lactams. Six-ring and larger ketones, lac-
tones, and lactams show the normal frequency found for the open-chain compounds.
5. Hydrogen bonding to a carbonyl group causes a shift to lower frequency of 40 to 60 cm−1.
Acids, amides, enolized b-keto carbonyl systems, and o-hydroxyphenol and o-aminophenyl
carbonyl compounds show this effect. All carbonyl compounds tend to give slightly lower
values for the carbonyl stretching frequency in the solid state compared with the value for
dilute solutions.
6. Where more than one of the structural influences on a particular carbonyl group is operating, the
net effect is usually close to additive.

TABLE 3.4 Absorption Frequencies of Carbonyl Bands

All bands quoted are strong.

 SPECTROSCOPY 3.13

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued)

Groups Band, cm−1 Remarks

(Continued)
3.14 SECTION THREE

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued)

Groups Band, cm−1 Remarks

 SPECTROSCOPY 3.15

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued)

Groups Band, cm−1 Remarks

3.16 SECTION THREE

TABLE 3.5 Absorption Frequencies of Other Double Bonds

Abbreviations Used in the Table

m, moderately strong vs, very strong
m–s, moderate to strong w, weak
var, of variable strength
 SPECTROSCOPY 3.17

TABLE 3.5 Absorption Frequencies of Other Double Bonds (Continued)

Group Band, cm−1 Remarks

Imines, oximes, and amidines C˙N[ (Continued)

(Continued)
3.18 SECTION THREE

TABLE 3.5 Absorption Frequencies of Other Double Bonds (Continued)

Group Band, cm−1 Remarks

Nitro compounds N˙O (Continued)

 SPECTROSCOPY 3.19

TABLE 3.6 Absorption Frequencies of Aromatic Bands

Abbreviations Used in the Table

m, moderately strong var, of variable strength
m–s, moderate to strong w–m, weak to moderately strong
s, srong
3.20 SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands

Abbreviations Used in the Table

m, moderately strong vs, very strong
m–s, moderate to strong w, weak
s, strong w–m, weak to moderately strong
var, of variable strength
 SPECTROSCOPY 3.21

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Sulfur compounds

(Continued)
3.22 SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Sulfur compounds (Continued)

 SPECTROSCOPY 3.23

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Phosphorus compounds (Continued)

(Continued)
3.24 SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Boron compounds (Continued)

 SPECTROSCOPY 3.25

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Halogen compounds (Continued)

(Continued)
3.26 SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued)

Group Band, cm−1 Remarks

Inorganic ions (Continued)

TABLE 3.8 Absorption Frequencies in the Near Infrared

Values in parentheses are molar absorptivity.

 SPECTROSCOPY 3.27

TABLE 3.8 Absorption Frequencies of the Near Infrared (Continued)

Class Band, cm−1 Remarks

(Continued)
3.28 SECTION THREE

TABLE 3.8 Absorption Frequencies of the Near Infrared (Continued)

Class Band, cm−1 Remarks

TABLE 3.9 Infrared Transmitting Materials

 SPECTROSCOPY 3.29

TABLE 3.9 Infrared Transmitting Materials (Continued)

* Usual for internal reflection work.

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents

Transmission below 80%, obtained with a 0.10-mm cell path, is shown as shaded area.

(Continued)
3.30 SECTION THREE

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents (Continued)

 SPECTROSCOPY 3.31

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents (Continued)

TABLE 3.11 Values of Absorbance for Percent Absorption

To convert percent absorption (% A) to absorbance, find the present absorption to the nearest whole digit in the
left-hand column; read across to the column located under the tenth of a percent desired, and read the value of
absorbance. The value of absorbance corresponding to 26.8% absorption is thus 0.1355.
3.32 SECTION THREE

TABLE 3.11 Values of Absorbance for Percent Absorption (Continued)

%A .0 .1 .2 .3 .4 .5 .6 .7 .8 .9
 SPECTROSCOPY 3.33

TABLE 3.11 Values of Absorbance for Percent Absorption (Continued)

%A .0 .1 .2 .3 .4 .5 .6 .7 .8 .9

TABLE 3.12 Transmittance-Absorbance Conversion Table

This table gives absorbance values to four significant figures corresponding to % transmittance values, which are
given to three significant figures. The values of % transmittance are given in the left-hand column and in the top
row. For example, 8.4% transmittance corresponds to an absorbance of 1.076.
Interpolation is facilitated and accuracy is maximized if the % transmittance is between 1 and 10, by multiply-
ing its value by 10, finding the absorbance corresponding to the result, and adding 1. For example, to find the
absorbance corresponding to 8.45% transmittance, note that 84.5% transmittance corresponds to an absorbance
of 0.0731, so that 8.45% transmittance corresponds to an absorbance of 1.0731. For % transmittance values
between 0.1 and 1, multiply by 100, find the absorbance corresponding to the result, and add 2.
Conversely, to find the % transmittance corresponding to an absorbance between 1 and 2, subtract 1 from the
absorbance, find the % transmittance corresponding to the result, and divide by 10. For example, an absorbance of
1.219 can best be converted to % transmittance by noting that an absorbance of 0.219 would correspond to 60.4%
transmittance; dividing this by 10 gives the desired value, 6.04% transmittance. For absorbance values between 2
and 3, subtract 2 from the absorbance, find the % transmittance corresponding to the result, and divide by 100.

(Continued)
3.34 SECTION THREE

TABLE 3.12 Transmittance-Absorbance Conversion Table (Continued)

%
Trans-
mittance 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 SPECTROSCOPY 3.35

TABLE 3.12 Transmittance-Absorbance Conversion Table (Continued)

%
Trans-
mittance 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
3.36 SECTION THREE

TABLE 3.13 Wavenumber/Wavelength Conversion Table

This table is based on the conversion: wavenumber (in cm−1) = 10,000/wavelength (in mm). For example, 15.4 mm
is equal to 649 cm−1.
 SPECTROSCOPY 3.37

3.2 RAMAN SPECTROSCOPY

Raman spectroscopy is the measurement of the wavelength and intensity of inelastically scattered
light from molecules. The Raman scattered light occurs at wavelengths that are shifted from the inci-
dent light by the energies of molecular vibrations.
The mechanism of Raman scattering is different from that of infrared absorption but Raman
and IR spectra provide complementary information for the identification of organic functionalities.
Raman spectra arise from the absorption of monochromatic light by a sample before it is emitted
as scattered light. As in infrared spectra, Raman spectra are recorded in wavenumbers. Frequently
a Raman spectrum will reveal something that was missed in the infrared spectrum. This is because
a bond that has no dipole moment (i.e., it is electrically symmetrical) will appear in the Raman
spectrum but will not appear in the infrared spectrum. Typical applications for Raman spec-
troscopy are in structure determination, multicomponent qualitative analysis, and quantitative
analysis.
The Raman scattering transition moment is:
R = < Xi ∂ a ∂ Xj >

where Xi and Xj are the initial and final states, respectively, and a is the polarizability of the molecule:

a = ao + (r−re)(da/dr) + ... higher terms

where r is the distance between atoms and ao is the polarizability at the equilibrium bond length, re.
Polarizability can be defined as the ease of which an electron cloud can be distorted by an external
electric field. Since ao is a constant and < Xi ∂ Xj > = 0, R simplifies to:

R = < Xi ∂ (r − re)(da/dr) ∂ Xj >

The result is that there must be a change in polarizability during the vibration for that vibration to
inelastically scatter radiation.
The polarizability depends on how tightly the electrons are bound to the nuclei. In the symmetric
stretch the strength of electron binding is different between the minimum and maximum internuclear
distances. Therefore the polarizability changes during the vibration and this vibrational mode scat-
ters Raman light (the vibration is Raman active). In the asymmetric stretch the electrons are more
easily polarized in the bond that expands but are less easily polarized in the bond that compresses.
There is no overall change in polarizability and the asymmetric stretch is Raman inactive.
Raman line intensities are proportional to:

ν⋅ s(ν) ⋅I⋅ exp(−Ei /kT) ⋅ C

where ν is the frequency of the incident radiation, s (ν) is the Raman cross section (typically 10−29 cm2),
I is the radiation intensity, exp(−Ei /kT) is the Boltzmann factor for state i, and C is the analyte
concentration.
3.38 SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon

Abbreviations Used in the Table

m, moderately strong
m–s, moderate to strong
m–vs, moderate to very strong
s, strong
vs, very strong
vw, very weak
w, weak
w–m, weak to moderately strong
w–vs, weak to very strong
 SPECTROSCOPY 3.39

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued)

Group Band, cm−1 Remarks

Saturated C[H and C[C (Continued)

(Continued)
3.40 SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued)

Group Band, cm−1 Remarks

Saturated C[H and C[C (Continued)

 SPECTROSCOPY 3.41

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued)

Group Band, cm−1 Remarks

Saturated C[H (Continued)

(Continued)
3.42 SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued)

Group Band, cm−1 Remarks

N[H and C[N Bonds (Continued)

TABLE 3.15 Raman Frequencies of Triple Bonds

Abbreviations Used in the Table

m, moderately strong s–vs, strong to very strong
m–s, moderate to strong vs, very strong
s, strong
 SPECTROSCOPY 3.43

TABLE 3.15 Raman Frequencies of Triple Bonds (Continued)

Group Band, cm−1 Remarks

TABLE 3.16 Raman Frequencies of Cumulated Double Bonds

Abbreviations Used in the Table

s, strong vw, very weak
vs, very strong w, weak

(Continued)
3.44 SECTION THREE

TABLE 3.16 Raman Frequencies of Cumulated Double Bonds (Continued)

Group Band, cm−1 Remarks

TABLE 3.17 Raman Frequencies of Carbonyl Bands

Abbreviations Used in the Table

m, moderately strong s–vs, strong to very strong
m–s, moderate to strong vs, very strong
s, strong w, weak
 SPECTROSCOPY 3.45

TABLE 3.17 Raman Frequencies of Carbonyl Bands (Continued)

Group Band, cm−1 Remarks

3.46 SECTION THREE

TABLE 3.18 Raman Frequencies of Other Double Bonds

Abbreviations Used in the Table

m, moderately strong vs, very strong
m–s, moderate to strong w, weak
s, strong s–vs, strong to very strong
w–m, weak to moderately strong
 SPECTROSCOPY 3.47

TABLE 3.18 Raman Frequencies of Other Double Bonds (Continued)

Group Band, cm−1 Remarks

(Continued)
3.48 SECTION THREE

TABLE 3.18 Raman Frequencies of Other Double Bonds (Continued)

Group Band, cm−1 Remarks

Nitroalkanes 1560–1548 (m–s) Sensitive to substitutes attached
Primary 1395–1370 (s) to CNO2 group
915–898 (m–s)
894–873 (m–s)
618–609 (w)
640–615 (w) Shoulder
494–472 (w–m) Broad; useful to distinguish
from secondary nitroalkanes
Secondary 1553–1547 (m)
1375–1360 (s)
908–868 (m)
863–847 (s)
625–613 (m)
560–516 (s) Sharp band
Tertiary 1543–1533 (m)
1355–1345 (s)
Nitrogen oxides
+ −
N→O 1612–1602 (s)
1252 (m)
1049–1017 (s)
835 (s)
541 (w)
469 (w)

TABLE 3.19 Raman Frequencies of Aromatic Compounds

Abbreviations Used in the Table

m, moderately strong
m–s, moderate to strong
m–vs, moderate to very strong
s, strong
s–vs, strong to very strong
var, of variable strength
vs, very strong
w, weak
w–m, weak to moderately strong
 SPECTROSCOPY 3.49

TABLE 3.19 Raman Frequencies of Aromatic Compounds (Continued)

Group Band, cm−1 Remarks

Substitution patterns of the benzene ring (Continued)

3.50 SECTION THREE

TABLE 3.20 Raman Frequencies of Sulfur Compounds

Abbreviations Used in the Table

m, moderately strong s–vs, strong to very strong
m–s, moderate to strong vs, very strong
s, strong w–m, weak to moderately srong
 SPECTROSCOPY 3.51

TABLE 3.20 Raman Frequencies of Sulfur Compounds (Continued)

Group Band, cm−1 Remarks

TABLE 3.21 Raman Frequencies of Ethers

Abbreviations Used in the Table

m, moderately strong var, of variable strength
s, strong vs, very strong

[O[O[ 800–770 (var)

3.52 SECTION THREE

TABLE 3.22 Raman Frequencies of Halogen Compounds

Abbreviations Used in the Table

m–s, moderate strong var, of variable strength
s, strong vs, very strong
 SPECTROSCOPY 3.53

TABLE 3.23 Raman Frequencies of Miscellaneous Compounds

Abbreviations Used in the Table

m–s, moderately strong vs, very strong
s, strong vvs, very very strong

TABLE 3.24 Principal Argon-Ion Laser Plasma Lines

(Continued)