Professional Documents
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Interpretation of Infrared
Spectra, A Practical Approach
John Coates
Coates Consulting, Newtown, USA
1 Introduction
2 The Origins of the Infrared Spectrum
3 Spectral Interpretation by Application of
Vibrational Group Frequencies
3.1 The Hydrocarbon Species and
Molecular Backbone
3.2 Simple Functional Groups
3.3 The Carbonyl Group
3.4 Other Functional Groups Associated
with Heteroatoms
3.5 Simple Inorganics
4 The Practical Situation Obtaining the
Spectrum and Interpreting the Results
4.1 Sample History
4.2 Physical Characteristics of the
Sample
4.3 The Chemistry of the Sample
4.4 The Infrared Sampling Method
5 An Overview to Infrared Spectral
Interpretation Some Simple Rules and
Guidelines
5.1 A Quick Diagnostic Assessment of
an Infrared Spectrum
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Related Articles
References
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1 INTRODUCTION
The qualitative aspects of infrared spectroscopy are one
of the most powerful attributes of this diverse and
versatile analytical technique. Over the years, much has
been published in terms of the fundamental absorption
frequencies (also known as group frequencies) which are
the key to unlocking the structure spectral relationships
of the associated molecular vibrations. Applying this
knowledge at the practical routine level tends to be
a mixture of art and science. While many purists will
argue against this statement, this author believes that it
is not possible to teach a person to become proficient as
an interpretive spectroscopist by merely presenting the
known relationships between structure and the observed
spectra. Instead, the practical approach, which has been
adopted in this text, is to help the reader appreciate the
visual aspects of the spectroscopy and how to interpret
these relative to the structure and chemistry of the sample.
This is achieved by recognizing characteristic shapes
and patterns within the spectrum, and by applying the
information obtained from published group frequency
data, along with other chemical and physical data from
the sample.
Included in the text is a discussion of the interrelationships that exist between the practical side of acquiring
the spectrum, the chemistry and physics of the sample
under study, the physical interactions of the sample with
its environment, and the impact of the structure on the
spectrum. In essence, the interpretation of infrared spectra is much more than simply assigning group frequencies.
The spectrum is rich in information, and this article is
intended to help the reader to extract the maximum
using the knowledge available for the sample and the
acquired spectral data. One important factor to bear in
2
mind is that a successful interpretation is based not only
on the presence of particular bands within the spectrum,
but also the absence of other important bands. Complete
classes of compounds can be rapidly excluded during the
interpretation by the use of no-band information.
It must be understood that this article addresses
the issue of infrared spectral interpretation from the
perspective of the average operator of an infrared
instrument. It is not a detailed treatise on the theory
of infrared spectroscopy where the modes of vibration
are discussed in terms of group theory, and where
mathematical models are used to compare theoretical
and observed values for the fundamental vibrations of a
molecule. There are many excellent texts that cover this
subject..1 4/ Instead, this article focuses on the day-today problems associated with characterizing a material or
attempting to perform some form of identification. One
of the main challenges in presenting a text on spectral
interpretation is to form a balance between the theory
that is needed to appreciate the links between molecular
structure and the observed spectrum and the practice.
For this reason, a minimum amount of relevant theory
is included in the next section, which provides a basic
understanding of why the spectrum exists, how it is
formed, and what factors contribute to the complexity
of observed spectra. It has been assumed that the reader
has a fundamental knowledge of molecular theory and
bonding, and that there is an understanding of basic
structures, in particular for organic compounds.
Infrared spectral interpretation may be applied to
both organic and inorganic compounds, and there are
many specialized texts dealing with these compounds, in
combination and as individual specialized texts. There
are too many to reference comprehensively, and the
reader is directed to a publication that provides a
bibliography of the most important reference texts..5/
However, the most informative general reference texts
are included,.6 14/ with books by Socrates.10/ and LinVien.11/ being recommended for general organics, and
by Nakamoto.13/ and Nyquist et al..14/ for inorganics
(salts and coordination compounds). There are numerous
specialized texts dealing with specific classes of materials,
and undoubtedly polymers and plastics form the largest
individual class..15 17/ In this particular case, texts by
Hummel and Scholl.16/ and Koenig.17/ provide a good
basic understanding.
The following comments are made relative to the conventions used within this article. The term frequency
is used for band/peak position throughout, and this is
expressed in the commonly used units of wavenumber (cm 1 ). The average modern infrared instrument
records spectra from an upper limit of around 4000 cm 1
(by convention) down to 400 cm 1 as defined by the
optics of the instrument (commonly based on potassium
INFRARED SPECTROSCOPY
frequency/energy
.2/
The fundamental requirement for infrared activity, leading to absorption of infrared radiation, is that there must
be a net change in dipole moment during the vibration
for the molecule or the functional group under study.
Another important form of vibrational spectroscopy is
Raman spectroscopy, which is complementary to infrared
spectroscopy. The selection rules for Raman spectroscopy
are different to those for infrared spectroscopy, and in
this case a net change in bond polarizability must be
observed for a transition to be Raman active. The remaining theoretical discussion in this article will be limited to a
very simple model for the infrared spectrum. The reader
is encouraged to refer to more complete texts.2 4/ for
detailed discussion of the fundamentals.
While it was stated that the fundamental infrared
absorption frequencies are not the only component to be
evaluated in a spectral interpretation, they are the essence
and foundation of the art. For the most part, the basic
model of the simple harmonic oscillator and its modification to account for anharmonicity suffice to explain the
origin of many of the characteristic frequencies that can
be assigned to particular combinations of atoms within
a molecule. From a simple statement of Hookes law we
can express the fundamental vibrational frequency of a
molecular ensemble according to Equation (3):
r
1
k
nD
.3/
2pc
where n D fundamental vibration frequency, k D force
constant, and D reduced mass. The reduced mass, D
m1 m2 /.m1 C m2 /, where m1 and m2 are the component
masses for the chemical bond under consideration.
This simple equation provides a link between the
strength (or springiness) of the covalent bond between
two atoms (or molecular fragments), the mass of the interacting atoms (molecular fragments) and the frequency of
vibration. Although simple in concept, there is a reasonably good fit between the bond stretching vibrations
predicted and the values observed for the fundamentals.
This simple model does not account for repulsion and
attraction of the electron cloud at the extremes of the
vibration, and does not accommodate the concept of
bond dissociation at high levels of absorbed energy. A
model incorporating anharmonicity terms is commonly
used to interpret the deviations from ideality and the
overall energy spatial relationship during the vibration
6 (nonlinear) .4/
5 (linear)
.5/
INFRARED SPECTROSCOPY
100
80
60
Q
40
20
Q
400
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
compounds may also show evidence of some fine structure when studied in the vapor state. For example, it is
common to observe the sharp feature (or spike) assigned
to the Q-branch of the vibrational rotational spectrum,
as indicated by the vapor spectrum of acetone (Figure 1).
If we proceed up the homologous series from methane
(CH4 ) to n-hexane (C6 H14 ), there are 20 component
atoms, which would imply 54 normal modes. In this case
the picture is slightly more complex. Methane is a unique
molecule, and only contains one type of C H group no
other types of bond exist in this molecule. In hexane there
are several types of bond and functionality. For reference,
a simple two-dimensional representation of the structure
is provided in Figure 2(a).
As we can see, there are two terminal methyl groups
(CH3 ) and four connecting methylene groups (CH2 ).
Each of these groups has its corresponding C H
stretching and bending vibrations (see later text for the
actual absorption frequencies). Also, the methyl groups
are linked to a neighboring methylene group, which is
in turn linked to neighboring methylene groups, and so
on. These linkages feature carbon carbon bonds. For
interpretation, we view the C H groups as functional
groups, giving rise to the common group frequencies,
and the C C linkages as the backbone, producing the
skeletal vibrations. As a rule, a group frequency may
be applied generally to most compounds featuring the
corresponding functional group. In contrast, the skeletal
vibrations are unique to a specific molecule. The group
frequencies help to characterize a compound, and the
Wavenumber (cm1)
Figure 1 Vapor spectrum of acetone with characteristic
Q-branch slitting, denoted by Q. Copyright Coates Consulting.
HH H H
H
H C C C H
H C C C H
H H H HH
(a)
HH
H C
H C
HH
(b)
H HH
C H
C
C H
H
HH
80
60
40
CH 3
(CH 2 )5
CH3
20
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
Figure 3 Attenuated total reflectance (ATR) spectrum of
n-heptane. Copyright Coates Consulting.
80
CH3
20
CH3
CH3
CH
CH3
1600
40
1800
60
CH2
CH3
600
800
1000
1200
1400
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
Figure 4 ATR spectrum of 2,2,4-trimethylpentane (isooctane).
Copyright Coates Consulting.
6
functional groups or the basic substructure. Such interactions can be severe, and result in overwhelming distortions
in the appearance of the spectrum, a good example
being hydrogen bonding. This will be dealt with in depth
later.
3 SPECTRAL INTERPRETATION BY
APPLICATION OF VIBRATIONAL
GROUP FREQUENCIES
This section includes tabulated data relative to the
most significant group frequencies for the most common
functional groups and structural components found in
organic compounds. Brief reference is also made to simple
inorganic compounds, in the form of simple ionic species.
More detailed listings can be found in published literature,
and the reader is encouraged to acquire one or more of
these reference texts..9 13/ As already indicated, the use
of tabulated data is only a part of the interpretation
process, and other facets of the spectrum must be taken
into account.
To help gain an understanding of infrared spectral
interpretation, it is instructive to start at the root of most
organic compounds, namely the fundamental backbone
or the parent hydrocarbon structure. We shall start with
the simple, aliphatic hydrocarbon, which is at the root
of most aliphatic compounds. Aliphatic hydrocarbons
exist in simple linear chains, branched chains and in
cyclic structures examples of the linear and branched
chain scenarios were provided earlier for hexane isomers.
Any one molecule may exist with one or more of these
component structures. The infrared spectrum can provide
information on the existence of most of these structures,
either directly or by inference.
The introduction of unsaturation in the form of a
double or triple bond has a profound impact on the
chemistry of the molecule, and likewise it has a significant
influence on the infrared spectrum. Similarly, the same is
observed when an aromatic structure is present within
a molecule. Infrared spectroscopy is a powerful tool
for identifying the presence of these functionalities. It
provides information specific to the group itself, and
also on the interaction of the group with other parts
of the molecule and on the spatial properties of the
group. Examples of these include conjugation between a
double bond and another unsaturated center, an aromatic
ring or a group, such as a carbonyl (CDO), and the
orientation or location of the double bond within the
molecule, such as cis or trans and medial or terminal. It
should be noted that cis/trans relationships are not specific
to unsaturated hydrocarbons, and the terminology is
referenced elsewhere, such as with secondary amide
structures. Again, the associated changes in the spatial
INFRARED SPECTROSCOPY
Origin
3040 3010
C H
1420 1410
1310 1290
C H
C H
970 960
700 (broad)
100
80
60
40
H
H
C C
(CH2)3
H
20
CH3
600
800
1000
1200
1400
1600
0
1800
Pendant (vinylidene) C H
stretch
Medial, cis- or trans-C H
stretch
Vinyl C H in-plane bend
Vinylidene C H in-plane
bend
Vinyl C H out-of-plane bend
Vinylidene C H out-of-plane
bend
trans-C H out-of-plane bend
cis-C H out-of-plane bend
2000
2400
2820 2780
C H
2800
2850 2815
Assignment
1680 1620
1625
1600
3095 3075
C3040 3010
3095 3075
3200
2900 2880
1350 1330
1300 700
CDC
3600
Group frequency,
wavenumber (cm 1 )
4000
Methyl (CH3 )
Methyl C H asym./sym. stretch
Methyl C H asym./sym. bend
gem-Dimethyl or iso- (doublet)
Trimethyl or tert-butyl (multiplet)
Methylene ( CH2 )
Methylene C H asym./sym. stretch
Methylene C H bend
Methylene (CH2 )n rocking
(n 3)
Cyclohexane ring vibrations
Methyne ( CH)
Methyne C H stretch
Methyne C H bend
Skeletal C C vibrations
Special methyl (CH3 ) frequencies
Methoxy, methyl ether O CH3 ,
C H stretch
Methylamino, N CH3 , C H stretch
Transmittance (%)
Functional group/assignment
Wavenumber (cm1)
Figure 5 ATR spectrum of 1-hexene. Copyright Coates Consulting.
INFRARED SPECTROSCOPY
1
1
1
1400
1200
1000
800
1400
1200
1000
800
1400
1200
1000
800
1600
1800
2000
2400
2800
3200
100
80
60
CH3
40
20
H
CH3
H
1800
1600
1800
1600
2000
(b)
2400
100
80
60
CH3
H
40
2000
2400
CH3
(c)
20
Wavenumber (cm1)
Figure 6 ATR spectra of xylene isomers: (a) o-xylene, 1,2dimethylbenzene; (b) m-xylene, 1,3-dimethylbenzene; (c) pxylene, 1,4-dimethylbenzene. Copyright Coates Consulting.
Table 4 Acetylenic (alkyne) group frequencies
Origin
3600
(a)
2800
CH3
2800
3200
20
3200
3600
Combib
CH3
40
3600
C H
60
4000
1615 1580
1510 1450
3130 3070
1225 950 (several)
4000
CDC Ca
CDC Ca
C H
C H
80
Assignment
4000
Group frequency,
wavenumber (cm 1 )
Transmittance (%)
Origin
100
Group frequency,
wavenumber (cm 1 )
CC
2140 2100
CC
2260 2190
C H
C H
C H
3320 3310
680 610
630 (typical)
Assignment
Terminal alkyne
(monosubstituted)
Medial alkyne
(disubstituted)
Alkyne C H stretch
Alkyne C H bend
Alkyne C H bend
(skeletal vibrations)
This increase in bond order produces a corresponding
increase in bond strength, which in turn increases the force
Group frequency,
wavenumber (cm 1 )a
C F
1150 1000
C Cl
800 700
C Br
700 600
C I
600 500
Assignment
Aliphatic fluoro compounds,
C F stretch
Aliphatic chloro compounds,
C Cl stretch
Aliphatic bromo compounds,
C Br stretch
Aliphatic iodo compounds,
C I stretch
Note that the ranges quoted serve as a guide only; the actual ranges
are influenced by carbon chain length, the actual number of halogen
substituents, and the molecular conformations present.
10
INFRARED SPECTROSCOPY
Group frequency,
wavenumber (cm 1 )
Assignment
O H
3400 3200
O H
3550 3450
3570 3540
3645 3600 (narrow)
O H
3645 3630
3635 3620
3620 3540
3640 3530a
1350 1260
1410 1310
720 590
C O 1050b
1100b
1150b
1200b
a
b
80
60
Cl
H
40
20
H
H
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
(a)
80
60
CH3
40
20
(b)
H
H
H
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
11
Transmittance (%)
100
50
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
4000
Wavenumber (cm1)
(a)
50
N H
N H
(b)
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
N H
C N
N H
Group frequency,
wavenumber (cm 1 )
3400 3380
C3345 3325
3510 3460
C3415 3380
1650 1590
1090 1020
3360 3310
Group frequency,
wavenumber (cm 1 )
Assignment
C H
2820 2810
C O C
1150 1050
C O C
1140 1070
f O H
1270 1230
Methoxy, C H stretch
(CH3 O )
Alkyl-substituted ether,
C O stretch
Cyclic ethers, large
rings, C O stretch
Aromatic ethers,
aryl O stretch
Epoxy and oxirane rings
Peroxides, C O O
stretch
C O
C O O C
a
Typically very weak, and not very characteristic in the infrared. Tend
to be more characteristic in the Raman spectrum.
3450
N H
3490 3430
DN H
3350 3320
N H
C N
1650 1550
1190 1130
C N
1210 1150
C N
1340 1250
C N
1350 1280
C N
1360 1310
Assignment
Primary amino
Aliphatic primary amine,
NH stretch
Aromatic primary amine,
NH stretch
Primary amine, NH bend
Primary amine, CN stretch
Secondary amino
Aliphatic secondary amine,
NH stretch
Aromatic secondary amine,
NH stretch
Heterocyclic amine,
NH stretch
Imino compounds,
NH stretch
Secondary amine, NH bend
Secondary amine,
CN stretch
Tertiary amino
Tertiary amine, CN stretch
Aromatic amino
Aromatic primary amine,
CN stretch
Aromatic secondary amine,
CN stretch
Aromatic tertiary amine,
CN stretch
12
100
80
60
NH2
H
40
H
20
H
H
600
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
4000
0
(a)
100
80
CH3
60
NH
H
40
20
H
H
1600
1400
1200
1000
800
600
1600
1400
1200
1000
800
600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
(b)
100
80
CH3
60
CH3
H
40
H
20
H
H
(c)
1800
2000
2400
2800
3200
3600
0
4000
INFRARED SPECTROSCOPY
Wavenumber (cm1)
13
20
CH 3 (CH 2 )2 C
400
800
OH
1200
1600
2000
2400
2800
2100 1800
3200
1680 1630
1690 1675/(1650 1600)a
1725 1700
1725 1705
1740 1725/(2800 2700)b
1750 1725
1735
1760 1740
1815 1770
1820 1775
1850 1800/1790 1740
1870 1820/1800 1775
3600
Functional group
4000
Transmittance (%)
Wavenumber (cm1)
Figure 10 Transmission spectrum of n-butyric acid. Copyright
Coates Consulting.
14
INFRARED SPECTROSCOPY
Functional group/assignment
2280 2240
2240 2220
2260 2240/1190 1080
Aliphatic cyanide/nitrile
Aromatic cyanide/nitrile
Cyanate ( OCN and C OCN
stretch)
Isocyanate ( NDCDO asym.
stretch)
Thiocyanate ( SCN)
Isothiocyanate ( NCS)
Open-chain imino ( CDN )
Open-chain azo ( NDN )
2276 2240
2175 2140
2150 1990
1690 1590
1630 1575
1110 1080
a
Functional group/assignment
Nitrogen-oxy compounds
Aliphatic nitro compounds
Aromatic nitro compounds
Organic nitrates
Phosphorus-oxy compounds
Organic phosphates (PDO
stretch)
Aliphatic phosphates
(P O C stretch)
Aromatic phosphates
(P O C stretch)
Sulfur-oxy compounds
Dialkyl/aryl sulfones
Organic sulfates
Sulfonates
Silicon-oxy compounds
Organic siloxane or silicone
(Si O Si)
Organic siloxane or silicone
(Si O C)
Functional group/assignment
Thiols (S H stretch)
Thiol or thioether, CH2 S
(C S stretch)
Thioethers, CH3 S (C S
stretch)
Aryl thioethers, f S (C S
stretch)
Disulfides (C S stretch)
Disulfides (S S stretch)
Aryl disulfides (S S stretch)
Polysulfides (S S stretch)
Functional group/assignment
Carbonate ion
Sulfate ion
Nitrate ion
Phosphate ion
Silicate ion
Ammonium ion
Cyanide ion, thiocyanate ion,
and related ions
Typically, the first absorption is intense and broad, and the second
has weak to medium intensity and is narrow. Both often exist as
multiple band structures, and this may be used to characterize individual
compounds.
15
2.
3.
4.
The sample is a complete known and the interpretation is required to confirm the material composition and/or quality examples include product
quality control and the confirmation of a structure or functionality of a newly synthesized material.
16
INFRARED SPECTROSCOPY
17
18
compounds will react with alcohols and amines to form
esters and amides. The formation of such derivatives is
common practice in the identification of organic compounds, and can be extremely informative in a definitive
identification by infrared spectroscopy. Other chemical
modifications that can be equally informative are for the
identification of olefinic or unsaturated compounds. A
simple reaction with bromine (caution use in solution,
or prepare in situ) will often confirm the presence of
a double bond. The reaction product can be helpful in
characterizing the nature of the unsaturation, especially
in the case of a cis configuration, which is often spectrally
masked by other absorptions in the region.
One similar modification, which is strictly not chemical
in nature, is deuterium exchange. In this case, a compound
with either a labile hydroxy group or an amino group is
placed in equilibrium with a deuterated solvent, such as
deuterium oxide (heavy water). The replacement of the
O H in the molecule by O D, in the case of hydroxy
compounds, can help in the confirmation of the hydroxy
group, and it can shift an overlapping hydroxy function
from the C H stretching and bending regions, thereby
assisting in the determination of the backbone structure.
Note that the shift induced by the replacement of O H
by O D is nearly as much as 1000 cm 1 .
Finally, an important chemical characteristic to be
understood is hydrogen bonding. The infrared spectrum
is a wonderful tool for helping to monitor the presence
of this phenomenon. However, one must be aware of
the fact that hydrogen bonding is usually concentration
dependent. If a hydroxy compound is examined in
a nonpolar solvent, one should be aware that the
hydroxy group spectrum, in particular bands assigned
to the stretching vibration, will change shape, position,
and intensity as a function of concentration. Also,
diagnostically, if the hydroxy group bands do not
change significantly with concentration, then this is a
strong indication of intramolecular (internal) hydrogen
bonding. This latter information is important in helping
to determine the spatial relationships of hydroxy groups
within a molecule.
The last two sections might seem to be obvious basic
knowledge in the chemistry and physical properties of a
material. However, just simple observations of the type
described can be invaluable in determining the presence
of specific functional groups when used in combination
with the infrared spectrum. Likewise, the use of negative
spectral information, viz. the absence of a characteristic
group frequency, is equally important. For example, if
a sample has an almond-like odor, but does not have
a strong band between 2200 and 2000 cm 1 , then the
compound is more likely to be a nitro compound or
benzaldehyde than a cyano compound. If an aldehydic
INFRARED SPECTROSCOPY
5 AN OVERVIEW TO INFRARED
SPECTRAL INTERPRETATION SOME
SIMPLE RULES AND GUIDELINES
This final section is a review of the ideas presented so far
as to how to go about the interpretation of an infrared
spectrum. With it, there is the implied understanding that
the infrared spectrum is only one source of information,
and additional information is most likely required for a
satisfactory analysis of the spectrum. The following are
a set of simple guidelines to help a person through the
early stages of rationalizing an infrared spectrum and to
19
20
INFRARED SPECTROSCOPY
80
60
40
20
800
1000
1200
1400
1600
1800
2000
2400
2800
3200
3600
0
4000
Transmittance (%)
100
Wavenumber (cm1)
Figure 11 ATR spectrum of a commercial solvent mixture
containing methanol, dichloromethane, toluene and acetone.
Copyright Coates Consulting.
21
22
For simple aromatic compounds, a series of weak
absorptions may be observed between 2000 and
1700 cm 1 . These are multiple combination bands that
are noticeably weak, and are typically not to be confused
with an isolated weak carbonyl absorption.
The C H bending vibrations can also be used to
support the presence of an aromatic structure. If there
are medium-to-strong absorptions, sometimes more than
one, between 850 and 670 cm 1 , these can be assigned to
C H out-of-plane bending on an aromatic ring. These
support the assignment of the 1600/1500 cm 1 bands, and
the locations of the bands are often indicative of the
nature of the substitution of the aromatic ring. For simple
structures, it is possible to differentiate mono-, di- (ortho,
meta and para), and certain poly-substitutions. Note that
a single, strong band may support simple ortho (around
750 cm 1 ) or para (around 830 cm 1 ) substitution.
Many organic compounds have multiple band structures in the region 1150 950 cm 1 . The in-plane C H
bending vibrations of aromatic compounds typically occur
in this region, and can exist as complex band structures (multiple, well-defined bands). They tend not to be
diagnostic for many compounds because of conflict and
overlap with other functional group absorptions, including some skeletal (backbone) vibrations. However, they
are clearly observable in simple hydrocarbons as weakto-moderate absorptions, and in halogen-substituted
aromatic compounds (such as chlorobenzenes) as characteristic strong absorptions.
5.1.7 Diagnostic Step 7: Testing for Multiple Bonding
(Often with a Bond Order of 2 or
Higher) Absorption in the Region
2300 1990 cm 1
Multiply bonded nitrogen compounds and cumulated
multiple bond compounds, such as cyanides (nitriles),
cyanates, isocyanates, thiocyanates, and diazo compounds, exhibit characteristic absorptions in the region
2300 1990 cm 1 . Cyanide absorptions vary from weak to
moderate to strong, depending on the nature of other
substituents in the molecule. Conjugation, including substitution on an aromatic ring, modifies the intensity of this
absorption.
If the absorption band is extremely strong, the group
is more likely to be a three-center functionality, such as a
cyanate, an isocyanate, or a thiocyanate.
Acetylenes and alkyne substituents also exhibit a weakto-moderate absorption within the same spectral region.
If the acetylenic function is internal (medial), then the
absorption can be extremely weak. However, a terminal
alkyne group (CC) band may have moderate intensity,
and this is supported by a characteristic C H stretching
absorption around 3310 cm 1 . A relatively low-frequency
INFRARED SPECTROSCOPY
RELATED ARTICLES
Infrared Spectroscopy (Volume 12)
Quantitative Analysis, Infrared Theory of Infrared
Spectroscopy
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