Infrared Spectroscopy

Infrared Spectroscopy is the analysis of infrared light interacting with a molecule. This can
be analyzed in three ways by measuring absorption, emission and reflection. The main use
of this technique is in organic and inorganic chemistry. It is used by chemists to determine
functional groups in molecules. IR Spectroscopy measures the vibrations of atoms, and
based on this it is possible to determine the functional groups.5 Generally, stronger bonds
and light atoms will vibrate at a high stretching frequency (wavenumber).

How an FTIR Spectrometer Operates

FTIR spectrometers (Fourier Transform Infrared Spectrometer) are widely used in organic
synthesis, polymer science, petrochemical engineering, pharmaceutical industry and food
analysis. In addition, since FTIR spectrometers can be hyphenated to chromatography, the
mechanism of chemical reactions and the detection of unstable substances can be
investigated with such instruments.

Introduction
The range of Infrared region is 12800 ~ 10 cm-1and can be divided into near-infrared
region (12800 ~ 4000 cm-1), mid-infrared region (4000 ~ 200 cm-1) and far-infrared
region (50 ~ 1000 cm-1). The discovery of infrared light can be dated back to the
19th century. Since then, scientists have established various ways to utilize infrared
light. Infrared absorption spectroscopy is the method which scientists use to
determine the structures of molecules with the molecules’ characteristic absorption
of infrared radiation. Infrared spectrum is molecular vibrational spectrum. When
exposed to infrared radiation, sample molecules selectively absorb radiation of
specific wavelengths which causes the change of dipole moment of sample
molecules. Consequently, the vibrational energy levels of sample molecules transfer
from ground state to excited state. The frequency of the absorption peak is
determined by the vibrational energy gap. The number of absorption peaks is related
to the number of vibrational freedom of the molecule. The intensity of absorption
peaks is related to the change of dipole moment and the possibility of the transition
of energy levels. Therefore, by analyzing the infrared spectrum, one can readily
obtain abundant structure information of a molecule. Most molecules are infrared
active except for several homonuclear diatomic molecules such as O2, N2 and Cl2 due
to the zero dipole change in the vibration and rotation of these molecules. What
makes infrared absorption spectroscopy even more useful is the fact that it is
capable to analyze all gas, liquid and solid samples. The common used region for
infrared absorption spectroscopy is 4000 ~ 400 cm-1 because the absorption
radiation of most organic compounds and inorganic ions is within this region.

FTIR spectrometers are the third generation infrared spectrometer. FTIR

spectrometers have several prominent advantages: (1) The signal-to-noise ratio of
spectrum is significantly higher than the previous generation infrared spectrometers.
(2) The accuracy of wavenumber is high. The error is within the range of ± 0.01 cm -
1
. (3) The scan time of all frequencies is short (approximately 1 s). (4) The resolution
is extremely high (0.1 ~ 0.005 cm-1). (5) The scan range is wide (1000 ~ 10 cm-1).
(6) The interference from stray light is reduced. Due to these advantages, FTIR
Spectrometers have replaced dispersive IR spectrometers.

Development of IR Spectrometers
Up till FTIR spectrometers, there have been three generations of IR spectrometers.

1. The first generation IR spectrometer was invented in late 1950s. It utilizes prism
optical splitting system. The prisms are made of NaCl. The requirement of the
sample’s water content and particle size is extremely strict. Further more, the scan
range is narrow. Additionally, the repeatability is fairly poor. As a result, the first
generation IR spectrometer is no longer in use.
2. The second generation IR spectrometer was introduced to the world in 1960s. It
utilizes gratings as the monochrometer. The performance of the second generation
IR spectrometer is much better compared with IR spectrometers with prism
monochrometer, But there are still several prominent weaknesses such as low
sensitivity, low scan speed and poor wavelength accuracy which rendered it out of
date after the invention of the third generation IR spectrometer.
3. The invention of the third generation IR spectrometer, Fourier transform infrared
spectrometer, marked the abdication of monochrometer and the prosperity of
interferometer. With this replacement, IR spectrometers became exceptionally
powerful. Consequently, various applications of IR spectrometer have been realized.

Dispersive IR Spectrometers
To understand the powerfulness and usefulness of FTIR spectrometer, it is essential
to have some background information of dispersive IR Spectrometer. The basic
components of a dispersive IR spectrometer include a radiation source,
monochromator, and detector. The common IR radiation sources are inert solids that
are heated electrically to promote thermal emission of radiation in the infrared
region of the electromagnetic spectrum. The monochromator is a device used to
disperse or separate a broad spectrum of IR radiation into individual narrow IR
frequencies.

Generally, dispersive spectrometers have a double-beam design with two equivalent

beams from the same source passing through the sample and reference chambers
as independent beams. These reference and sample beams are alternately focused
on the detector by making use of an optical chopper, such as, a sector mirror. One
beam will proceed, traveling through the sample, while the other beam will pass
through a reference species for analytical comparison of transmitted photon
wavefront information.

After the incident radiation travels through the sample species, the emitted
wavefront of radiation is dispersed by a monochromator (gratings and slits) into its
component frequencies. A combination of prisms or gratings with variable-slit
mechanisms, mirrors, and filters comprise the dispersive system. Narrower slits gives
better resolution by distinguishing more closely spaced frequencies of radiation and
wider slits allow more light to reach the detector and provide better system
sensitivity. The emitted wavefront beam (analog spectral output) hits the detector
and generates an electrical signal as a response.

Detectors are devices that convert the analog spectral output into an electrical
signal. These electrical signals are further processed by the computer using
mathematical algorithm to arrive at the final spectrum. The detectors used in IR
spectrometers can be classified as either photon/quantum detectors or thermal
detectors.

It is the absorption of IR radiation by the sample, producing a change of IR radiation

intensity, which gets detected as an off-null signal (e.g. different from reference
signal). This change is translated into the recorder response through the actions of
synchronous motors. Each frequency that passes through the sample is measured
individually by the detector which consequently slows the process of scanning the
entire IR region. A block diagram of a classic dispersive IR spectrometer is shown
in Figure 1.

Figure 1. Simplified representation of a dispersive IR spectrometer.

FTIR Spectrometers
The Components of FTIR Spectrometers
A common FTIR spectrometer consists of a source, interferometer, sample
compartment, detector, amplifier, A/D convertor, and a computer. The source
generates radiation which passes the sample through the interferometer and
reaches the detector. Then the signal is amplified and converted to digital signal by
the amplifier and analog-to-digital converter, respectively. Eventually, the signal is
transferred to a computer in which Fourier transform is carried out. Figure 2 is a
block diagram of an FTIR spectrometer.

Figure 2. Block diagram of an FTIR spectrometer

The major difference between an FTIR spectrometer and a dispersive IR

spectrometer is the Michelson interferometer.

Michelson Interferometer
The Michelson interferometer, which is the core of FTIR spectrometers, is used to
split one beam of light into two so that the paths of the two beams are different.
Then the Michelson interferometer recombines the two beams and conducts them
into the detector where the difference of the intensity of these two beams are
measured as a function of the difference of the paths. Figure 3 is a schematic of
the Michelson Interferometer.
 Figure 3. Schematic of the Michelson interferometer

A typical Michelson interferometer consists of two perpendicular mirrors and a

beamsplitter. One of the mirror is a stationary mirror and another one is a movable
mirror. The beamsplitter is designed to transmit half of the light and reflect half of
the light. Subsequently, the transmitted light and the reflected light strike the
stationary mirror and the movable mirror, respectively. When reflected back by the
mirrors, two beams of light recombine with each other at the beamsplitter.

If the distances travelled by two beams are the same which means the distances
between two mirrors and the beamsplitter are the same, the situation is defined as
zero path difference (ZPD). But imagine if the movable mirror moves away from the
beamsplitter, the light beam which strikes the movable mirror will travel a longer
distance than the light beam which strikes the stationary mirror. The distance which
the movable mirror is away from the ZPD is defined as the mirror displacement and
is represented by ∆. It is obvious that the extra distance travelled by the light which
strikes the movable mirror is 2∆. The extra distance is defined as the optical path
difference (OPD) and is represented by delta. Therefore,

δ=2Δ(1)(1)δ=2Δ
It is well established that when OPD is the multiples of the wavelength, constructive
interference occurs because crests overlap with crests, troughs with troughs. As a result, a
maximum intensity signal is observed by the detector. This situation can be described by the
following equation:
 δ=nλ(2)(2)δ=nλ

with n = 0,1,2,3...

In contrast, when OPD is the half wavelength or half wavelength add multiples of
wavelength, destructive interference occurs because crests overlap with troughs.
Consequently, a minimum intensity signal is observed by the detector. This situation
can be described by the following equation:

δ=(n+12)λ(3)(3)δ=(n+12)λ
with n = 0,1,2,3...

These two situations are two extreme situations. If the OPD is neither n-fold
wavelengths nor (n+1/2)-fold wavelengths, the interference should be between
constructive and destructive. So the intensity of the signal should be between
maximum and minimum. Since the mirror moves back and forth, the intensity of the
signal increases and decreases which gives rise to a cosine wave. The plot is defined
as an interferogram. When detecting the radiation of a broad band source rather
than a single-wavelength source, a peak at ZPD is found in the interferogram. At the
other distance scanned, the signal decays quickly since the mirror moves back and
forth. Figure 4(a) shows an interferogram of a broad band source.

Fourier Transform of Interferogram to Spectrum

The interferogram is a function of time and the values outputted by this function of
time are said to make up the time domain. The time domain is Fourier transformed
to get a frequency domain, which is deconvolved to product a spectrum. Figure
4 shows the Fast Fourier transform from an interferogram of polychromatic light to
its spectrum.

(a)
(b)
 Figure 4. (a) Interferogram of a monochromatic light; (b) its spectrum

The Fourier Transform

The first one who found that a spectrum and its interferogram are related via a
Fourier transform was Lord Rayleigh. He made the discover in 1892. But the first
one who successfully converted an interferogram to its spectrum was Fellgett who
made the accomplishment after more than half a century. Fast Fourier transform
method on which the modern FTIR spectrometer based was introduced to the world
by Cooley and Turkey in 1965. It has been applied widely to analytical methods such
as infrared spectrometry, nuclear magnetic resonance and mass spectrometry due to
several prominent advantages which are listed in Table 1.

Table 1. Advantages of Fourier Transform over Continuous-Wave Spectrometry

Fourier transform, named after the French mathematician and physicist Jean
Baptiste Joseph Fourier, is a mathematical method to transform a function into a
new function. The following equation is a common form of the Fourier transform
with unitary normalization constants:

F(ω)=12π−−√∫∞−∞f(t)e−iωtdt(4)(4)F(ω)=12π∫−∞∞f(t)e−iωtdt
in which t is time, i is the square root of -1.

The following equation is another form of the Fourier transform(cosine transform)

which applies to real, even functions:

F(ν)=12π−−√∫∞−∞f(t)cos(2πνt)dt(5)(5)F(ν)=12π∫−∞∞f(t)cos⁡(2πνt)dt

The following equation shows how f(t) is related to F(v) via a Fourier transform:

f(t)=12π−−√∫∞−∞F(ν)cos(2πνt)dν(6)(6)f(t)=12π∫−∞∞F(ν)cos⁡(2πνt)dν

An Alternative Explanation of the Fourier

Transform in FTIR Spectrometers
The math description of the Fourier transform can be tedious and confusing. An
alternative explanation of the Fourier transform in FTIR spectrometers is provided
here before we jump into the math description to give you a rough impression which
may help you understand the math description.

The interferogram obtained is a plot of the intensity of signal versus OPD. A Fourier
transform can be viewed as the inversion of the independent variable of a function.
Thus, Fourier transform of the interferogram can be viewed as the inversion of OPD.
The unit of OPD is centimeter, so the inversion of OPD has a unit of inverse
centimeters, cm-1. Inverse centimeters are also known as wavenumbers. After the
Fourier transform, a plot of intensity of signal versus wavenumber is produced. Such
a plot is an IR spectrum. Although this explanation is easy to understand, it is not
perfectly rigorous.

Simplified Math Description of the Fourier

Transform in FTIR
The wave functions of the reflected and transmitted beams may be represented by
the general form of:

E1=rtcEm×cos(νt−2πkx)(7)(7)E1=rtcEm×cos⁡(νt−2πkx)

and
 E1=rtcEm×cos[νt−2πk(νx+Δd)](8)(8)E1=rtcEm×cos[νt−2πk(νx+Δd)]

Where

 ΔdΔd is the path difference,

 rr = reflectance (amplitude) of the beam splitter,
 tt is the transmittance, and
 cc is the polarization constant.

The resultant wave function of their superposition at the detector is represented as:

E=E1+E2=2(r×t×c×Em)×cos(νt−2πkx)cos(πkΔd)(9)(9)E=E1+E2=2(r×t×c×Em)×cos⁡(
νt−2πkx)cos⁡(πkΔd)

Where Em,, ν, and k are the amplitude, frequency and wave number of the IR
radiation source.

The intensity (I) detected is the time average of E2 and is written as

I=4r2t2c2E2mcos2(νt−2πkx)cos2(πkΔd)(10)(10)I=4r2t2c2Em2cos2(νt−2πkx)cos2(πkΔd)
Since the time average of the first cosine term is just ½, then

I=2I(k)cos2(πkΔd)(11)(11)I=2I(k)cos2⁡(πkΔd)
and

I(Δd)=I(k)[1+cos(2πkΔd)](12)(12)I(Δd)=I(k)[1+cos⁡(2πkΔd)]
where I(k) is a constant that depends only upon k and I(∆d) is the interferogram.

From I(∆d) we can get I(k) using Fourier transform as follows:

I(Δd)−I(∞)=∫km0I(k)cos(2ΠkΔd)dk(13)(13)I(Δd)−I(∞)=∫0kmI(k)cos⁡(2ΠkΔd)dk

Letting Km →∞, we can write

I(k)=∫∞0[I(Δd)−I(∞)]cos(2ΠkΔd)dΔd(14)(14)I(k)=∫0∞[I(Δd)−I(∞)]cos⁡(2ΠkΔd)dΔd
The physically measured information recorded at the detector produces an interferogram,
which provides information about a response change over time within the mirror scan
distance. Therefore, the interferogram obtained at the detector is a time domain spectrum.
This procedure involves sampling each position, which can take a long time if the signal is
small and the number of frequencies being sampled is large.
In terms of ordinary frequency, νν, the Fourier transform of this is given by (angular
frequency ω=sπνω=sπν):

f(ν)=∫∞−∞f(t)e−i2Πνtdt(15)(15)f(ν)=∫−∞∞f(t)e−i2Πνtdt
The inverse Fourier transform is given by:

f(ν)=∫∞−∞f(t)e+i2πνtdt(16)(16)f(ν)=∫−∞∞f(t)e+i2πνtdt

The interferogram is transformed into IR absorption spectrum (Figure 5) that is

commonly recognizable with absorption intensity or % transmittance plotted against
the wavelength or wavenumber. The ratio of radiant power transmitted by the
sample (I) relative to the radiant power of incident light on the sample (I0) results in
quantity of Transmittance, (T). Absorbance (A) is the logarithm to the base 10 of the
reciprocal of the transmittance (T):

A=log101T=−log10T=−log10II0(17)(17)A=log101T=−log10T=−log10II0

Figure 5. IR spectrum of a sample

Hands-on Operation of an FTIR Spectrometer

Step 1: The first step is sample preparation. The standard method to prepare solid sample
for FTIR spectrometer is to use KBr. About 2 mg of sample and 200 mg KBr are
dried and ground. The particle size should be unified and less than two micrometers.
Then, the mixture is squeezed to form transparent pellets which can be measured
directly. For liquids with high boiling point or viscous solution, it can be added in
between two NaCl pellets. Then the sample is fixed in the cell by skews and
measured. For volatile liquid sample, it is dissolved in CS2 or CCl4 to form 10%
solution. Then the solution is injected into a liquid cell for measurement. Gas sample
needs to be measured in a gas cell with two KBr windows on each side. The gas cell
should first be vacuumed. Then the sample can be introduced to the gas cell for
measurement.

Step 2: The second step is getting a background spectrum by collecting an

interferogram and its subsequent conversion to frequency data by inverse Fourier
transform. We obtain the background spectrum because the solvent in which we
place our sample will have traces of dissolved gases as well as solvent molecules
that contribute information that are not our sample. The background spectrum will
contain information about the species of gases and solvent molecules, which may
then be subtracted away from our sample spectrum in order to gain information
about just the sample. Figure 6 shows an example of an FTIR background
spectrum.

Figure 6. Background IR spectrum

The background spectrum also takes into account several other factors related to the
instrument performance, which includes information about the source,
interferometer, detector, and the contribution of ambient water (note the two
irregular groups of lines at about 3600 cm–1 and about 1600 cm–1 in Figure 6) and
carbon dioxide (note the doublet at 2360 cm–1 and sharp spike at 667 cm–1 in Figure
6) present in the optical bench.

Step 3: Next, we collect a single-beam spectrum of the sample, which will contain
absorption bands from the sample as well as the background (gaseous or solvent).

Step 4: The ratio between the single-beam sample spectrum and the single beam
background spectrum gives the spectrum of the sample (Figure 7).

Figure 7. Sample IR spectrum

Step 5: Data analysis is done by assigning the observed absorption frequency bands
in the sample spectrum to appropriate normal modes of vibrations in the molecules.

Portable FTIR Spectrometers

Despite of the powerfulness of traditional FTIR spectrometers, they are not suitable
for real-time monitoring or field use. So various portable FTIR spectrometers have
been developed. Below are two examples.

Ahonen et al developed a portable, real-time FTIR spectrometer as a gas analyzer

for industrial hygiene use. The instrument consists of an operational keyboard, a
control panel, signal and control processing electronics, an interferometer, a
heatable sample cell and a detector. All the components were packed into a cart. To
minimize the size of the instrument, the resolution of FTIR spectrometer was
sacraficed. But it is good enough for the use of industrial hygiene. The correlation
 coefficient of hygienic effect between the analyzer and adsorption tubes is about 1
mg/m3.

Korb et al developed a portable FTIR spectrometer which only weighs about 12.5 kg
so that it can be held by hand. Moreover, the energy source of the instrument is
battery so that the mobility is significantly enhanced. Besides, the instrument can
function well within the temperature range of 0 to 45 oC and the humidity range of 0
to 100%. Additionally, this instrument resists vibration. It works well in an operating
helicopter. Consequently, this instrument is excellent for the analysis of radiation
from the surface and atmosphere of the Earth. The instrument is also very stable.
After a three-year operation, it did not lose optical alignment. The reduction of size
was implemented by a creative design of optical system and accessory components.
Two KBr prisms were used to constitute the interferometer cavity. Optical coatings
replaced the mirrors and beam splitter in the interferometer. The optical path is
shortened with a much more compact packaging of components. A small, low
energy consuming interferometer drive was designed. It is also mass balanced to
resist vibration. The common He-Ne tube was replaced by a smaller laser diode.

Infrared: Application
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Infrared spectroscopy, an analytical technique that takes advantage of the vibrational

transitions of a molecule, has been of great significance to scientific researchers in many
fields such as protein characterization, nanoscale semiconductor analysis and space
exploration.

Introduction
Infrared spectroscopy is the study of interaction of infrared light with matter, which can be
used to identify unknown materials, examine the quality of a sample or determine the amount
of components in a mixture. Infrared light refers to electromagnetic radiation with
wavenumber ranging from 13000 – 10 cm-1 (corresponding wavelength from 0.78 – 1000
μm). Infrared region is further divided into three subregions: near-infrared (13000 – 4000 cm-
1
or 0.78 – 2.5 μm), mid-infrared (4000 – 400 cm-1 or 2.5 – 25 μm) and far-infrared (400 – 10
cm-1 or 25 – 1000 μm). The most commonly used is the middle infrared region, since
molecules can absorb radiations in this region to induce the vibrational excitation of
functional groups. Recently, applications of near infrared spectroscopy have also been
developed.

By passing infrared light through a sample and measuring the absorption or transmittance of
light at each frequency, an infrared spectrum is obtained, with peaks corresponding to the
frequency of absorbed radiation. Since all groups have their characteristic vibrational
frequencies, information regarding molecular structure can be gained from the spectrum.
Infrared spectroscopy is capable of analyzing samples in almost any phase (liquid, solid, or
gas), and can be used alone or in combination with other instruments following different
sampling procedures. Besides fundamental vibrational modes, other factors such as overtone
and combination bands, Fermi resonance, coupling and vibration-rotational bands also appear
in the spectrum. Due to the high information content of its spectrum, infrared spectroscopy
has been a very common and useful tool for structure elucidation and substance
identification.

Instrumentation
Most commonly used instruments in infrared spectroscopy are dispersive infrared
spectrometer and Fourier transform infrared spectrometer.

Dispersive infrared spectrometer

Dispersive infrared spectrometer is mainly composed of radiation source, monochromator
and detector. For mid-infrared region, Globar (silicon carbide), Nernst glower (oxides of
zirconium, yttrium and erbium) and metallic helices (chromium-nickel alloy or tungsten) are
frequently used as radiation sources. Tungsten-halogen lamps and metallic conductors coated
with ceramic are utilized as sources for near-infrared region. A mercury high-pressure lamp is
suitable for far-infrared region.

Monochromator in conjunction with slits, mirrors and filters separates the wavelengths of
light emitted. The dispersive elements within monochromator are prisms or gratings. Gratings
have gradually replaced prisms due to their comparatively low cost and good quality. As
shown in Figure 1, radiation passes through both a sample and a reference path. Then the
beams are directed to a diffraction grating (splitter), which disperses the light into component
frequencies and directs each wavelength through a slit to the detector. The detector produces
an electrical signal and results in a recorder response.

Figure 1. Schematic illustration of dispersive infrared spectrometer. Figure from Wikipedia.

Two types of detectors are employed in dispersive infrared spectrometer, namely, thermal
detectors and photon detectors. Thermal detectors include thermocouples, thermistors, and
pneumatic devices, which measure the heating effect generated by infrared radiation. Photon
detectors are semiconductor-based. Radiation is able to promote electrons in photon detectors
from valence band to conduction band, generating a small current. Photon detectors have
faster response and higher sensitivity than do thermal detectors but are more susceptible to
thermal noise.

Fourier transform infrared spectrometer

Dispersive infrared spectrometer has many limitations because it examines component
frequencies individually, resulting in slow speed and low sensitivity. Fourier transform
infrared (FTIR) spectrometer is preferred over dispersive spectrometer, since it is capable of
handling all frequencies simultaneously with high throughput, reducing the time required for
analysis. The radiation sources used in dispersive infrared spectrometer can also be used in
FTIR spectrometer.

In contrast with the monochromator in dispersive spectrometer, FTIR spectrometer as shown

in Figure 2 employs an interferometer. The beamsplitter within the interferometer splits the
incoming infrared beam into two beams, one of which is reflected by a fixed mirror, while the
other one reflected by a moving mirror perpendicular to the fixed one. The length of path one
beam travels is fixed and that of the other one is changing as the mirror moves, generating an
optical path difference between the two beams. After meeting back at the beamsplitter,
the two beams recombine, interfere with each other, and yield an interferogram. The
interferogram produces inference signal as a function of optical path difference. It is
converted to a spectrum of absorbance or transmittance versus wavenumber or frequency by
Fourier transform.

Figure 2. Schematic representation of Fourier transform infrared spectrometer. Figure from

Wikipedia.

Detectors used in FTIR spectrometers are mainly pyroelectric and photoconductive detectors.
The former are constructed of crystalline materials (such as deuterated triglycine sulfate)
whose electric polarization rely on temperature. The change in temperature leads to change in
charge distribution of the detector and electric signal is produced. The latter (such as mercury
cadmium telluride) provide better sensitivity and faster speed than do pyroelectric detectors
over a broad spectral range. However, liquid nitrogen is needed for cooling of
photoconductive detectors.

Application
Since different molecules with different combination of atoms produce their unique spectra,
infrared spectroscopy can be used to qualitatively identify substances. In addition, the
intensity of the peaks in the spectrum is proportional to the amount of substance present,
enabling its application for quantitative analysis.
Qualitative analysis
For qualitative identification purposes, the spectrum is commonly presented as transmittance
versus wavenumber. Functional groups have their characteristic fundamental vibrations
which give rise to absorption at certain frequency range in the spectrum (Figure 3).

Figure 3.Infrared spectrum of 1-hexanol.

Each band in a spectrum can be attributed to stretching or bending mode of a bond. Almost
all the fundamental vibrations appear in the mid-infrared region. For instance, 4000 – 2500
cm-1 region usually can be assigned to stretching modes of O-H, N-H or C-H. Triple-
bond stretching modes appear in the region of 2500 – 2000 cm-1. C=C and C=O stretching
bands fall in the 2000 – 1500 cm-1 region. Hence, characterization of functional groups in
substances according to the frequencies and intensities of absorption peaks is feasible, and
also structures of molecules can be proposed. This method is applicable to organic molecules,
inorganic molecules, polymers, etc. A detailed frequency list of functional groups is shown
in Figure 4. Note that several functional groups may absorb at the same frequency range, and
a functional group may have multiple-characteristic absorption peaks, especially for 1500 –
650 cm-1, which is called the fingerprint region.

Figure 4. Characteristic infrared absorption frequencies.

Bands in the near-infrared region are overtones or combination bands. They are weak in
intensity and overlapped, making them not as useful for qualitative analysis as those in mid-
infrared region. However, absorptions in this region are helpful in exploiting information
related to vibrations of molecules containing heavy atoms, molecular skeleton vibrations,
molecular torsions and crystal lattice vibrations.

Besides structural elucidation, another qualitative application of infrared spectroscopy is the

identification of a compound with a reference infrared spectrum. If all the peaks of the
unknown match those of the reference, the compound can be identified. Additional reference
spectra are available online at databases such as NIST Chemistry WebBook.

Quantitative analysis
Absorbance is used for quantitative analysis due to its linear dependence on concentration.
Given by Beer-Lambert law, absorbance is directly proportional to the concentration and
pathlength of sample:

A=ϵclA=ϵcl
 where A is absorbance, ε the molar extinction coefficient or molar absorptivity which is
characteristic for a specific substance, c the concentration and l the pathlength (or the
thickness) of sample. The conversion from transmittance to absorbance is given by

A=−logTA=−log⁡T

where T is transmittance.

For quantitative analysis of liquid samples, usually an isolated peak with high molar
absorptivity that appears in the spectrum of the compound is chosen. A calibration curve of
absorbance at the chosen frequency against concentration of the compound is acquired by
measuring the absorbance of a series of standard compound solution with known
concentrations. These data are then graphed to get a linear plot, from which the concentration
of the unknown can be calculated after measuring its absorbance at the same frequency. The
number of functional groups can also be calculated in this way, since the molar absorptivity
of the band is proportional to the number of functional groups that are present in the
compound.

For solid samples, an internal standard with a constant known amount is added to the
unknown sample and the standards. Then similar procedures as those with liquid samples are
carried out except that the calibration curve is a graph of the ratio of absorbance of analyte to
that of the internal standard versus concentration of the analyte.

A multi-component analysis of the mixture is also feasible since different components have
different values of molar absorptivity at the same frequency.

However, infrared spectroscopy may be more susceptible to deviation from Beer's law than is
UV-Vis spectroscopy because of its narrow bands, complex spectra, weak incident beam, low
transducer sensitivity and solvent absorption.

Infrared: Theory
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Infrared (IR) spectroscopy is one of the most common and widely used spectroscopic
techniques employed mainly by inorganic and organic chemists due to its usefulness in
determining structures of compounds and identifying them. Chemical compounds have
different chemical properties due to the presence of different functional groups.
Introduction
Infrared (IR) spectroscopy is one of the most common and widely used spectroscopic
techniques. Absorbing groups in the infrared region absorb within a certain wavelength
region. The absorption peaks within this region are usually sharper when compared with
absorption peaks from the ultraviolet and visible regions. In this way, IR spectroscopy can be
very sensitive to determination of functional groups within a sample since different functional
group absorbs different particular frequency of IR radiation. Also, each molecule has a
characteristic spectrum often referred to as the fingerprint. A molecule can be identified by
comparing its absorption peak to a data bank of spectra. IR spectroscopy is very useful in the
identification and structure analysis of a variety of substances, including both organic and
inorganic compounds. It can also be used for both qualitative and quantitative analysis of
complex mixtures of similar compounds.

The use of infrared spectroscopy began in the 1950's by Wilbur Kaye. He had designed a
machine that tested the near-infrared spectrum and provided the theory to describe the results.
Karl Norris started using IR Spectroscopy in the analytical world in the 1960's and as a result
IR Spectroscopy became an accepted technique. There have been many advances in the field
of IR Spec, the most notable was the application of Fourier Transformations to this technique
thus creating an IR method that had higher resolution and a decrease in noise. The year this
method became accepted in the field was in the late 1960's.4

Absorption Spectroscopy
There are three main processes by which a molecule can absorb radiation. and each of these
routes involves an increase of energy that is proportional to the light absorbed. The first route
occurs when absorption of radiation leads to a higher rotational energy level in a rotational
transition. The second route is a vibrational transition which occurs on absorption of
quantized energy. This leads to an increased vibrational energy level. The third route involves
electrons of molecules being raised to a higher electron energy, which is the electronic
transition. It’s important to state that the energy is quantized and absorption of radiation
causes a molecule to move to a higher internal energy level. This is achieved by alternating
the electric field of the radiation interacting with the molecule and causing a change in the
movement of the molecule. There are multiple possibilities for the different possible energy
levels for the various types of transitions.

The energy levels can be rated in the following order: electronic > vibrational > rotational.
Each of these transitions differs by an order of magnitude. Rotational transitions occur at
lower energies (longer wavelengths) and this energy is insufficient and cannot cause
vibrational and electronic transitions but vibrational (near infra-red) and electronic transitions
(ultraviolet region of the electromagnetic spectrum) require higher energies.
Figure 1: Energy levels for a molecule. Possible transitions that occur: (A): Pure rotational
Transitions, (B) rotational-Vibrational Transitions, (C) Rotational-Vibrational-Electronic
Transitions

The energy of IR radiation is weaker than that of visible and ultraviolet radiation, and so the
type of radiation produced is different. Absorption of IR radiation is typical of molecular
species that have a small energy difference between the rotational and vibrational states. A
criterion for IR absorption is a net change in dipole moment in a molecule as it vibrates or
rotates. Using the molecule HBr as an example, the charge distribution between hydrogen
and bromine is not evenly distributed since bromine is more electronegative than hydrogen
and has a higher electron density. HBrHBr thus has a large dipole moment and is thus polar.
The dipole moment is determined by the magnitude of the charge difference and the distance
between the two centers of charge. As the molecule vibrates, there is a fluctuation in its
dipole moment; this causes a field that interacts with the electric field associated with
radiation. If there is a match in frequency of the radiation and the natural vibration of the
molecule, absorption occurs and this alters the amplitude of the molecular vibration. This also
occurs when the rotation of asymmetric molecules around their centers results in a dipole
moment change, which permits interaction with the radiation field.

Molecules such as O2, N2, Br2, do not have a changing dipole moment (amplitude nor
orientation) when they undergo rotational and vibrational motions, as a result, they
cannot cannot absorb IR radiation.

Diatomic Molecular Vibration

The absorption of IR radiation by a molecule can be likened to two atoms attached to each
other by a massless spring. Considering simple diatomic molecules, only one vibration is
possible. The Hook's law potential on the other hand is based on an ideal spring
 F=−kx(1.1)(1.1)F=−kx

F(x)=−dV(x)dx(1.2)(1.2)F(x)=−dV(x)dx

this results in one dimensional space

V(r)=12k(r−req)(1.3)(1.3)V(r)=12k(r−req)

One thing that the Morse and Harmonic have in common is the small displacements (x) from
the equilibrium. Solving the Schrödinger equation for the harmonic oscillator potential results
in the energy levels results in

Ev=(v+12)hve(1.4)(1.4)Ev=(v+12)hve

with v=0,1,2,3.....infinity

ve=12πkμ−−√(1.5)(1.5)ve=12πkμ

When calculating the energy of a diatomic molecule, factors such as anharmonicity (has a
similar curve with the harmonic oscillator at low potential energies but deviates at higher
energies) are considered. The energy spacing in the harmonic oscillator is equal but not so
with the anharmonic oscillator. The anharmonic oscillator is a deviation from the harmonic
oscillator. Other considered terms include; centrifugal stretching, vibrational and rotational
interactions have to be taken into account. The energy can be expressed mathematically as

Ev=(v+12)hveHarmonic Oscillator−(v+12)2Xehveanharmonicity+BeJ(J+1)Rigid
Rotor−DeJ2(J+1)2centrifugal stretching−αe(v+12)J(J+1)rovibrational
coupling(1.6)(1.6)Ev=(v+12)hveHarmonic Oscillator−(v+12)2Xehveanharmonicity+BeJ(J+1)Rigid
Rotor−DeJ2(J+1)2centrifugal stretching−αe(v+12)J(J+1)rovibrational coupling

The first and third terms represent the harmonicity and rigid rotor behavior of a
diatomic molecule such as HCl. The second term represents anharmonicity and the fourth
term represents centrifugal stretching. The fifth term represents the interaction between the
vibration and rotational interaction of the molecule.

Polyatomic Molecular Vibration

The bond of a molecule experiences various types of vibrations and rotations. This causes
the atom not to be stationary and to fluctuate continuously. Vibrational motions are defined
by stretching and bending modes. These movements are easily defined for diatomic or
triatomic molecules. This is not the case for large molecules due to several vibrational
motions and interactions that will be experienced. When there is a continuous change in the
interatomic distance along the axis of the bond between two atoms, this process is known as a
stretching vibration. A change in the angle occurring between two bonds is known as a
bending vibration. Four bending vibrations exist namely, wagging, twisting, rocking and
scissoring. A CH2 group is used as an example to illustrate stretching and bending vibrations
below.

Symmetric Stretch Asymmetric

Stretch Twisting

Wagging Scissoring Rockin

g

Figure 3: Types of Vibrational Modes. To ensure that no center of mass motion occurs, the
center atom (yellow ball) will also move. Figure from Wikipedia

As stated earlier, molecular vibrations consist of stretching and bending modes. A molecule
consisting of (N) number of atoms has a total of 3N degrees of freedom, corresponding to the
Cartesian coordinates of each atom in the molecule. In a non-linear molecule, 3 of these
degrees of freedom are rotational, 3 are translational and the remainder is fundamental
vibrations. In a linear molecule, there are 3 translational degrees of freedom and 2 are
rotational. This is because in a linear molecule, all of the atoms lie on a single straight line
and hence rotation about the bond axis is not possible. Mathematically the normal modes for
a linear and non linear can be expressed as

Linear Molecules: (3N - 5) degrees of freedom

Non-Linear molecules: (3N - 6) degrees of freedom

EXAMPLE 1: VIBRATIONS OF WATER

Diagram of Stretching and Bending Modes for H2O.

SOLUTION

H2O molecule is a non-linear molecule due to the uneven distribution of the electron density.
O2 is more electronegative than H2 and carries a negative charge, while H has a partial
positive charge. The total degrees of freedom for H2O will be 3(3)-6 = 9-6 = 3 degrees of
freedom which correspond to the following stretching and bending vibrations. The vibrational
modes are illustrated below:

Figure 4 The vibrational modes of H2O

EXAMPLE VIBRATIONS OF CO2CO2

Diagram of Stretching and Bending Modes for CO2.

SOLUTION

CO2 is a linear molecule and thus has the formula (3N-5). It has 4 modes of vibration (3(3)-5).
CO2 has 2 stretching modes, symmetric and asymmetric. The CO2 symmetric stretch is not IR
active because there is no change in dipole moment because the net dipole moments are in
opposite directions and as a result, they cancel each other. In the asymmetric stretch, O atom
moves away from the C atom and generates a net change in dipole moments and hence
absorbs IR radiation at 2350 cm-1. The other IR absorption occurs at 666 cm-1. CO2 symmetry
with D∞hD∞h CO2 has a total of four of stretching and bending modes but only two are seen.
Two of its bands are degenerate and one of the vibration modes is symmetric hence it does
not cause a dipole moment change because the polar directions cancel each other. The
vibrational modes are illustrated below:

Figure 5 The vibrational modes of CO2

The Deduction of Frequency

The second law of Newton states that

F=ma(1.7)(1.7)F=ma

where m is the mass and a is the acceleration, acceleration is a 2nd order differential equation
of distance with respect to time. Thus "a" can be written as

a=d2ydt(1.8)(1.8)a=d2ydt

Substituting this into equation 1 gives

md2ydt2=−ky(1.9)(1.9)md2ydt2=−ky

the 2nd order differential equation of this equation is equal to −km−km displacement of mass
and time can be stated as

y=Acos2πνmt(1.10)(1.10)y=Acos⁡2πνmt

where vm is the natural vibrational frequency and A is the maximum amplitude of the
motion. On differentiating a second time the equation becomes

d2ydt2=−4π2ν2mAcos2πνmtd2ydt2=−4π2νm2Acos⁡2πνmt

substituting the two equations above into Newton's second law for a harmonic oscillator,
m∗(−4π2ν2mAcos 2πνmt)=−k∗(Acos 2πνmt)(1.11)(1.11)m∗(−4π2νm2Acos 2πνmt)=−k∗(Aco
s 2πνmt)

If we cancel out the two functions yy,

4mπ2ν2m=k(1.12)(1.12)4mπ2νm2=k

from above, we obtain the natural frequency of the oscillation.

νm=12πkm−−−√(1.13)(1.13)νm=12πkm

Vm which is the natural frequency of the mechanical oscillator which depends on the force
constant of the spring and the mass of the attached body and independent of energy imparted
on the system. when there are two masses involved in the system then the mass used in the
above equation becomes

μ=m1m2m1+m2(1.14)(1.14)μ=m1m2m1+m2

The vibrational frequency can be rewritten as

νm=12πkμ−−√(1.15)(1.15)νm=12πkμ

The Deduction of Wave Number

Using the harmonic oscillator and wave equations of quantum mechanics, the energy can be
written as

E=(v+12)h2πkμ−−√(1.16)(1.16)E=(v+12)h2πkμ

where h is Planck's constant and v is the vibrational quantum number and ranges from
0,1,2,3.... infinity.

E=(v+12)hvm(1.17)(1.17)E=(v+12)hvm

where νmνm is the vibrational frequency. Transitions in vibrational energy levels can be
brought about by absorption of radiation, provided the energy of the radiation exactly
matches the difference in energy levels between the vibrational quantum states and provided
the vibration causes a change in dipole moment. This can be expressed as

△E=hvm=h2πkμ−−√(1.18)(1.18)△E=hvm=h2πkμ

At room temperature, the majority of molecules are in the ground state v = 0, from the
equation above

Eo=12hvm(1.19)(1.19)Eo=12hvm
following the selection rule, when a molecule absorbs energy, there is a promotion to the first
excited state

E1=32hvm(1.20)(1.20)E1=32hvm

(32hvm−12hvm)=hvm(1.21)(1.21)(32hvm−12hvm)=hvm

The frequency of radiation v that will bring about this change is identical to the classical
vibrational frequency of the bond vm and it can be expressed as

Eradiation=hv=△E=hvm=h2πkμ−−√(1.22)(1.22)Eradiation=hv=△E=hvm=h2πkμ

The above equation can be modified so that the radiation can be expressed in wave numbers

ν˜=h2πckμ−−√(1.23)(1.23)ν~=h2πckμ

where

 cc is the velocity of light (cm s-1) and

 ν˜ν~ is the wave number of an absorption maximum (cm-1)

Theory of IR
Molecular vibrational frequencies lie in the IR region of the electromagnetic spectrum, and
they can be measured using the IR technique. In IR, polychromatic light (light having
different frequencies) is passed through a sample and the intensity of the transmitted light is
measured at each frequency. When molecules absorb IR radiation, transitions occur from a
ground vibrational state to an excited vibrational state (Figure 1).

For a molecule to be IR active there must be a change in dipole moment as a result of the
vibration that occurs when IR radiation is absorbed. Dipole moment is a vector quantity and
depends on the orientation of the molecule and the photon electric vector. The dipole moment
changes as the bond expands and contracts. When all molecules are aligned as in a
crystal and the photon vector points along a molecular axis such as z. Absorption occurs for
the vibrations that displace the dipole along z. Vibrations that are totally x or y polarized
would be absent. Dipole moment in a heteronuclear diatomic molecule can be described as
uneven distribution of electron density between the atoms. One atom is more electronegative
than the other and has a net negative charge.

The dipole moment can be expressed mathematically as

μ=erμ=er

The relationship between IR intensity and dipole moment is given as

IIR∝(dμdQ)2IIR∝(dμdQ)2
 relating this to intensity of the IR radiation, we have have the following equation below.

where μμ is the dipole moment and QQ is the vibrational coordinate. The transition moment
integral, that gives information about the probability of a transition occurring, for IR can
also be written as

⟨ψ|M^|ψf⟩⟨ψ|M^|ψf⟩

ii and ff represent are initial and final states. ψiψi is the wave function. Relating this to
IR intensity we have

IIR∝⟨ψ|M^|ψf⟩IIR∝⟨ψ|M^|ψf⟩

where M^M^ is the dipole moment and has the Cartesian

coordinates, Mx^Mx^,My^My^, Mz^Mz^. In order for a transition to occur by dipole
selection rules , at least one of the integrals must be non zero.

Region of IR
The IR region of the electromagnetic spectrum ranges in wavelength from 2 -15 µm.
Conventionally the IR region is subdivided into three regions, near IR, mid IR and far IR.
Most of the IR used originates from the mid IR region. The table below indicates the IR
spectral regions

Wavelength Wavenumbers (V), cm-1 Freq

0.78 -2.5 12800 - 4000 3.8

2.5 - 50 4000 - 200 3.8

50 -100 200 -10 3.8

2.5 -15 4000 -670 3.8

IR deals with the interaction between a molecule and radiation from the electromagnetic
region ranging (4000- 40 cm-1). The cm-1 is the wave number scale and it can also be defined
as 1/wavelength in cm. A linear wavenumber is often used due to its direct relationship with
both frequency and energy. The frequency of the absorbed radiation causes the molecular
vibrational frequency for the absorption process. The relationship is given below
v¯(cm−1)=1λ(μm)×104(μmcm)=v(Hz)c(cm/s)(1.24)(1.24)v¯(cm−1)=1λ(μm)×104(μmcm)=v
(Hz)c(cm/s)

 Near InfraRed Spectroscopy: Absorption bands in the near infrared (NIR) region (750 - 2500
nm) are weak because they arise from vibrational overtones and combination bands.
Combination bands occur when two molecular vibrations are excited simultaneously. The
intensity of overtone bands reduces by one order of overtone for each successive overtone.
When a molecule is excited from the ground vibrational state to a higher vibrational state
and the vibrational quantum number v is greater than or equal to 2 then an overtone
absorption results. The first overtone results from v = 0 to v = 2. The second overtone occurs
when v =0 transitions to v = 3. Transitions arising from the near ir absorption are weak,
hence they are referred to as forbidden transitions but these transitions are relevant when
non-destructive measurements are required such as a solid sample. Near IR spectra though
have low absorption they have a high signal to noise ratio owing to intense radiation sources
and NIR is able to penetrate undiluted samples and use longer path lengths; it becomes very
useful for rapid measurement of more representative samples.
 Far InfraRed Spectroscopy: The far IR region is particularly useful for inorganic studies due
to stretching and bending vibrations of bonds between the metal atoms and ligands. The
frequencies, which these vibrations are observed, are usually lower than 650 cm -1. Pure
rotational absorption of gases is observed in the far IR region when there is a permanent
dipole moment present. Examples include H2O, O3, HCl.

IR Analysis
Qualitative Analysis
IR spectroscopy is a great method for identification of compounds, especially for
identification of functional groups. Therefore, we can use group frequencies for structural
analysis. Group frequencies are vibrations that are associated with certain functional groups.
It is possible to identify a functional group of a molecule by comparing its vibrational
frequency on an IR spectrum to an IR stored data bank.

Here, we take the IR spectrum of Formaldehyde for an example. Formaldehyde has a C=O
functional group and C-H bond. The value obtained from the following graph can be
compared to those in reference data banks stored for Formaldehyde. A molecule with a
C=O stretch has an IR band which is usually found near 1700 cm-1 and around 1400 cm-1 for
CH2 bend. It's important to note that this value is dependent on other functional groups
present on the molecule. The higher 1700 cm-1 indicates a large dipole moment change. It is
easier to bend a molecule than stretch it, hence stretching vibrations have higher frequencies
and require higher energies than bending modes. The finger print region is a region from
1400-650 cm-1. Each molecule has it's own characteristic print and is often cumbersome to
attach any values to this region.
 Figure 6 IR Spectrum of Formaldehyde

Quantitative Analysis
Infrared spectroscopy can also be applied in the field of quantitative analysis, although
sometimes it's not as accurate as other analytical methods, like gas chromatography and
liquid chromatography. The main theory of IR quantification is Beer's law or Beer-Lambert
law, which is written as

A=log(I0I)=ϵlc(1.25)(1.25)A=log⁡(I0I)=ϵlc

Where A is the absorbance of the sample, I is the intensity of transmitted light, I0 is the
intensity of incident light, l is the path length, a is the molar absorptivity of the substance, and
c is the concentration of the substance.

From the Beer's Law, we could figure out the relation between the absorbance and the
concentration of the sample since the analytes have a particular molar absorptivity at a
particular wavelength. Therefore, we could use IR spectroscopy and Beer's Law to find the
concentration of substance or the components of mixture. This is how the IR quantification
operated.

Selection Rules of IR
In order for vibrational transitions to occur, they are normally governed by some rules
referred to as selection rules.
 1. An interaction must occur between the oscillating field of the electromagnetic radiation and
the vibrational molecule for a transition to occur. This can be expressed mathematically as

(dμdr)req≠0(dμdr)req≠0

△v=+1△v=+1 and △J=+1△J=+1

2. This holds for a harmonic oscillator because the vibrational levels are equally
spaced and that accounts for the single peak observed in any given molecular vibration. For
gases J changes +1 for the R branch and -1 for the P branch.△J=0△J=0 is a forbidden
transition and hence a q branch for a diatomic will not be present. For any anharmonic
oscillator, the selection rule is not followed and it follows that the change in energy becomes
smaller. This results in weaker transitions called overtones, then △v=+2△v=+2 (first
overtone) can occur, as well as the 2nd overtone △v=+3△v=+3. The frequencies of the
1st and 2nd overtones provides information about the potential surface and about two to
three times that of the fundamental frequency.
3. For a diatomic, since μμ is known, measurement of ue provides a value for k, the force
constant.

k=(d2V(r)dr2)reqk=(d2V(r)dr2)req

where k is the force constant and indicates the strength of a bond.

Influence Factors of IR
 Isotope Effects: It's been observed that the effect on k when an atom is replaced by an
isotope is negligible but it does have an effect on νν due to changes in the new mass. This is
because the reduced mass has an effect on the rotational and vibrational behavior.
 Solvent Effects: The polarity of solvent will have an influence on the IR spectra of organic
compounds due to the interactions between solvent and compounds, which is called solvent
effects. If we place a compound, which contains n, pi and pi* orbitals, into a polar solvent,
the solvent will stabilizes these three orbitals in different extent. The stabilization effects of
polar solvent on n orbital is the largest one, the next larger one is pi* orbital, and the effects
on pi orbital is the smallest one. The spectra of n→pi* transition will shift to blue side, which
means it will move to shorter wavelengths and higher energies since the polar solvent
causes the energy difference between n orbital and pi* orbital to become bigger. The
spectra of pi→pi* transition will shift to red side, which means it will move to longer
wavelengths and lower energies since the polar solvent causes the energy difference
between n orbital and pi* orbital to become smaller.

Advantages of IR
 High Scan Speed: Infrared spectroscopy can get information for the whole range of
frequency simultaneously, within one second. Therefore, IR can be used to analyze a
substance that is not very stable and finish the scan before it start to decompose.
 High Resolution: The resolution of general prism spectrometer is only about 3 cm-1, but the
resolution of infrared spectrometer is much higher. For example, the resolution of Grating
 infrared spectrometer could be 0.2 cm-1, the resolution of FT infrared spectrometer could be
0.1-0.005 cm-1.
 High Sensitivity: With Fourier Transform, the infrared spectrometer doesn't need to use the
slit and monochromator. In this way, the reflection specularity will be increased and the loss
of energy in the analysis process will be decreased. Therefore the energy that reaches the
detector is large enough and even very small amount of analytes could be detected.
Nowadays, the infrared spectroscopy could detect the sample as small as 1-10 grams.
 Wide Range of Application: Infrared spectroscopy could be used to analyze almost all
organic compounds and some inorganic compounds. It has a wide range of application in
both qualitative analysis and quantitative analysis. Also, the sample of Infrared spectroscopy
doesn't have phase constraints. It could be gas, liquid or solid, which has enlarged the range
of analytes a lot.
 Large Amount of Information: Infrared Spectra could give us lots of structural information of
the analytes, such as the type of compound, the functional group of compound, the
stereoscopic structure of compound, the number and position of substituent group and so
on. Depending on the available information form the functional part and the fingerprint
part, infrared spectroscopy has become a great method to identify different kinds of
compounds.
 Non-Destructive: Infrared Spectroscopy is non-destructive to the sample.

Disadvantages of IR
 Sample Constraint: Infrared spectroscopy is not applicable to the sample that contains
water since this solvent strongly absorb IR light.
 Spectrum Complication: The IR spectrum is very complicated and the interpretation
depends on lots of experience. Sometimes, we cannot definitely clarify the structure of the
compound just based on one single IR spectrum. Other spectroscopy methods, such as (
Mass Spectrometry) MS and ( Nuclear Magnetic Resonance) NMR, are still needed to
further interpret the specific structure.
 Quantification: Infrared spectroscopy works well for the qualitative analysis of a large
variety of samples, but quantitative analysis may be limited under certain conditions such as
very high and low concentrations.

Symmetry & IR Spectroscopy

One of the most importance applications of IR spectroscopy is structural assignment of the
molecule depending on the relationship between the molecule and observed IR absorption
bands. Every molecule is corresponding to one particular symmetry point group. Then we can
predict which point group the molecule is belonging to if we know its IR vibrational bands.
Vice versa, we can also find out the IR active bands from the spectrum of the molecule if we
know its symmetry. These are two main applications of group theory. We'll take the
following problem as an example to illustrate how this works.

Question
How do you distinguish whether the structure of transition metal complex molecule
M(CO)2L4 is cis or trans by inspection of the CO stretching region of the IR spectra?
 Answer
For cis-M(CO)2L4, the symmetry point group of this molecule is C2v.

C2v E C2 σσ(xz) σσ(yz)

γγco 2 0 2 0

γγco = A1 + B1

Since A1 has a basis on z axis and B1 has a basis on x axis, there are two IR vibrational
bands observed in the spectrum.

For trans-M(CO)2L4, the symmetry point group of this molecule is D4h.

D4h E C4 C2 C2' C2" i S4 σhσh σvσv σdσd

γγco 2 2 2 0 0 0 0 0 2 2

γγco = A1g + A2u

Since A2u has a basis on z axis, there is only one IR vibrational band observed in the
spectrum.

Therefore, from what have been discussed above, we can distinguish these two structures
based on the number of IR bands.

Problems
The frequency of C=O stretching is higher than that of C=C stretching. The Intensity of C=O
stretching is stronger than that of C=C stretching. Explain it.

IR Spectroscopy Background
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This page describes what an infra-red spectrum is and how it arises from bond vibrations
within organic molecules.

How an infra-red spectrum is produced

You probably know that visible light is made up of a continuous range of different
electromagnetic frequencies - each frequency can be seen as a different color. Infra-red
radiation also consists of a continuous range of frequencies - it so happens that our eyes can't
detect them.

If you shine a range of infra-red frequencies one at a time through a sample of an organic
compound, you find that some frequencies get absorbed by the compound. A detector on the
other side of the compound would show that some frequencies pass through the compound
with almost no loss, but other frequencies are strongly absorbed.

How much of a particular frequency gets through the compound is measured as percentage
transmittance. A percentage transmittance of 100 would mean that all of that frequency
passed straight through the compound without any being absorbed. In practice, that never
happens - there is always some small loss, giving a transmittance of perhaps 95% as the best
you can achieve. A transmittance of only 5% would mean that nearly all of that particular
frequency is absorbed by the compound. A very high absorption of this sort tells you
important things about the bonds in the compound.

What an infra-red spectrum looks like

A graph is produced showing how the percentage transmittance varies with the frequency of
the infra-red radiation.
Notice that an unusual measure of frequency is used on the horizontal axis. Wavenumber is
defined like this:

Similarly, don't worry about the change of scale half-way across the horizontal axis. You will
find infra-red spectra where the scale is consistent all the way across, infra-red spectra where
the scale changes at around 2000 cm-1, and very occasionally where the scale changes again at
around 1000 cm-1. As you will see when we look at how to interpret infra-red spectra, this
does not cause any problems - you simply need to be careful reading the horizontal scale.

What causes some frequencies to be

absorbed?
Each frequency of light (including infra-red) has a certain energy. If a particular frequency is
being absorbed as it passes through the compound being investigated, it must mean that its
energy is being transferred to the compound.

Energies in infra-red radiation correspond to the energies involved in bond vibrations.

Bond stretching
In covalent bonds, atoms aren't joined by rigid links - the two atoms are held together because
both nuclei are attracted to the same pair of electrons. The two nuclei can vibrate backwards
and forwards - towards and away from each other - around an average position.

The diagram shows the stretching that happens in a carbon-oxygen single bond. There will, of
course, be other atoms attached to both the carbon and the oxygen. For example, it could be
the carbon-oxygen bond in methanol, CH3OH.

The energy involved in this vibration depends on things like the length of the bond and the
mass of the atoms at either end. That means that each different bond will vibrate in a different
way, involving different amounts of energy.

Bonds are vibrating all the time, but if you shine exactly the right amount of energy on a
bond, you can kick it into a higher state of vibration. The amount of energy it needs to do this
will vary from bond to bond, and so each different bond will absorb a different frequency
(and hence energy) of infra-red radiation.

Bond bending
As well as stretching, bonds can also bend. The diagram shows the bending of the bonds in a
water molecule. The effect of this, of course, is that the bond angle between the two
hydrogen-oxygen bonds fluctuates slightly around its average value. Imagine a lab model of a
water molecule where the atoms are joined together with springs. These bending vibrations
are what you would see if you shook the model gently.
Again, bonds will be vibrating like this all the time and, again, if you shine exactly the right
amount of energy on the bond, you can kick it into a higher state of vibration. Since the
energies involved with the bending will be different for each kind of bond, each different
bond will absorb a different frequency of infra-red radiation in order to make this jump from
one state to a higher one.

Tying all this together

Look again at the infra-red spectrum of propan-1-ol, CH3CH2CH2OH:

In the diagram, three sample absorptions are picked out to show you the bond vibrations
which produced them. Notice that bond stretching and bending produce different troughs in
the spectrum.
 Identifying the Presence of Particular
Groups
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This page explains how to use an infra-red spectrum to identify the presence of a few simple
bonds in organic compounds.

The infrared spectrum for a simple

carboxylic acid: Ethanoic acid
Ethanoic acid has the structure:

You will see that it contains the following bonds:

 carbon-oxygen double, C=O

 carbon-oxygen single, C-O
 oxygen-hydrogen, O-H
 carbon-hydrogen, C-H
 carbon-carbon single, C-C

The carbon-carbon bond has absorptions which occur over a wide range of wavenumbers in
the fingerprint region - that makes it very difficult to pick out on an infra-red spectrum. The
carbon-oxygen single bond also has an absorbtion in the fingerprint region, varying between
1000 and 1300 cm-1 depending on the molecule it is in. You have to be very wary about
picking out a particular trough as being due to a C-O bond.

The other bonds in ethanoic acid have easily recognized absorptions outside the fingerprint
region.

 The C-H bond (where the hydrogen is attached to a carbon which is singly-bonded to
everything else) absorbs somewhere in the range from 2853 - 2962 cm-1. Because that bond
 is present in most organic compounds, that's not terribly useful! What it means is that you
can ignore a trough just under 3000 cm-1, because that is probably just due to C-H bonds.
 The carbon-oxygen double bond, C=O, is one of the really useful absorptions, found in the
range 1680 - 1750 cm-1. Its position varies slightly depending on what sort of compound it is
in.
 The other really useful bond is the O-H bond. This absorbs differently depending on its
environment. It is easily recognised in an acid because it produces a very broad trough in the
range 2500 - 3300 cm-1.

The infrared spectrum for ethanoic acid looks like this:

The possible absorption due to the C-O single bond is queried because it lies in the
fingerprint region. You couldn't be sure that this trough wasn't caused by something else.

The infrared spectrum for an alcohol:

Ethanol
The O-H bond in an alcohol absorbs at a higher wavenumber than it does in an acid -
somewhere between 3230 - 3550 cm-1. In fact this absorption would be at a higher number
still if the alcohol isn't hydrogen bonded - for example, in the gas state. All the infra-red
spectra on this page are from liquids - so that possibility will never apply.

Notice the absorption due to the C-H bonds just under 3000 cm-1,
and also the troughs between 1000 and 1100 cm-1 - one of which
will be due to the C-O bond.

The infrared spectrum for an ester: Ethyl

ethanoate

This time the O-H absorption is missing completely. Don't confuse it with the C-H trough
fractionally less than 3000 cm-1. The presence of the C=O double bond is seen at about 1740
cm-1.

The C-O single bond is the absorption at about 1240 cm-1. Whether or not you could pick that
out would depend on the detail given by the table of data which you get in your exam,
because C-O single bonds vary anywhere between 1000 and 1300 cm-1 depending on what
sort of compound they are in. Some tables of data fine it down, so that they will tell you that
an absorption from 1230 - 1250 is the C-O bond in an ethanoate.
The infrared spectrum for a ketone:
Propanone

You will find that this is very similar to the infra-red spectrum for ethyl ethanoate, an ester.
Again, there is no trough due to the O-H bond, and again there is a marked absorption at
about 1700 cm-1 due to the C=O.

Confusingly, there are also absorptions which look as if they might be due to C-O single
bonds - which, of course, aren't present in propanone. This reinforces the care you have to
take in trying to identify any absorptions in the fingerprint region. Aldehydes will have
similar infra-red spectra to ketones.

The infrared spectrum for a hydroxy-acid:

2-hydroxypropanoic acid (lactic acid)
This is interesting because it contains two different sorts of O-H bond - the one in the acid
and the simple "alcohol" type in the chain attached to the -COOH group.

The O-H bond in the acid group absorbs between 2500 and 3300, the one in the chain
between 3230 and 3550 cm-1. Taken together, that gives this immense trough covering the
whole range from 2500 to 3550 cm-1. Lost in that trough as well will be absorptions due to the
C-H bonds. Notice also the presence of the strong C=O absorption at about 1730 cm-1.

The infrared spectrum for a primary

amine: 1-aminobutane

Primary amines contain the -NH2 group, and so have N-H bonds. These absorb somewhere
between 3100 and 3500 cm-1. That double trough (typical of primary amines) can be seen
clearly on the spectrum to the left of the C-H absorptions.
 Infrared: Interpretation
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Table of contents

Infrared spectroscopy is the study of the interaction of infrared light with matter. The
fundamental measurement obtained in infrared spectroscopy is an infrared spectrum, which is
a plot of measured infrared intensity versus wavelength (or frequency) of light.

Introduction
In infrared spectroscopy, units called wavenumbers are normally used to denote different
types of light. The frequency, wavelength, and wavenumber are related to each other via the
following equation(1):

(1)

These equations show that light waves may be described by their frequency, wavelength or
wavenumber. Here, we typically refer to light waves by their wavenumber, however it will be
more convenient to refer to a light wave's frequency or wavelength. The wavenumber of
several different types of light are shown in table 1.
 Table 1. The Electromagnetic spectrum showing the wavenumber of several different types
of light.

When a molecule absorbs infrared radiation, its chemical bonds vibrate. The bonds can
stretch, contract, and bend. This is why infrared spectroscopy is a type of vibrational
spectroscopy. Fortunately, the complex vibrational motion of a molecule can be broken down
into a number of constituent vibrations called normal modes. For example, when a guitar
string is plucked, the string vibrates at its normal mode frequency. Molecules, like guitar
strings, vibrate at specfic frequencies so different molecules vibrate at different frequencies
because their structures are different. This is why molecules can be distinguished using
infrared spectroscopy. The first necessary condition for a molecule to absorb infrared light is
that the molecule must have a vibration during which the change in dipole moment with
respect to distance is non-zero. This condition can be summarized in equation(2) form as
follows:

(2)

Vibrations that satisfy this equation are said to be infrared active. The H-Cl stretch of
hydrogen chloride and the asymmetric stretch of CO2 are examples of infrared active
vibrations. Infrared active vibrations cause the bands seen in an infrared spectrum.

The second necessary condition for infrared absorbance is that the energy of the light
impinging on a molecule must equal a vibrational energy level difference within the
molecule. This condition can be summarized in equation(3) form as follows:
 (3)

If the energy of a photon does not meet the criterion in this equation, it will be transmitted by
the sample and if the photon energy satisfies this equation, that photon will be absorbed by
the molecule.(See Infrared: Theory for more detail)

As any other analytical techniques, infrared spectroscopy works well on some samples, and
poorly on others. It is important to know the strengths and weaknesses of infrared
spectroscopy so it can be used in the proper way. Some advantages and disadvantages of
infrared spectroscopy are listed in table 2.

Advantages Disadvantages

Solids, Liquids, gases, semi- Atoms or monatomic ions

solids, powders and polymers do not have infrared
are all analyzed spectra

The peak positions, Homonuclear diatomic

intensities, widths, and molecules do not posses
shapes all provide useful infrared spectra
information
Complex mixture and
Fast and easy technique aqueous solutions
are difficult to analyze
Sensitive using infrared
technique (Micrograms of spectroscopy
materials can be detected
routinely)

Inexpensive

Table 2. The Advantage and Disadvantage of Infrared Spectroscopy

Origin of Peak Positions, Intensities, and
Widths
Peak Positions
The equation(4) gives the frequency of light that a molecule will absorb, and gives the
frequency of vibration of the normal mode excited by that light.

(4)

Only two variables in equation(4) are a chemical bond's force constant and reduced mass.
Here, the reduced mass refers to (M1M2)/(M1+M2) where M1 and M2 are the masses of the two
atoms, respectively. These two molecular properties determine the wavenumber at which a
molecule will absorb infrared light. No two chemical substances in the universe have the
same force constants and atomic masses, which is why the infrared spectrum of each
chemical substance is unique. To understand the effect of atomic masses and force constant
on the positions of infrared bands, table 3 and 4 are shown as an example, respectively.

Table 3. An Example of
an Mass Effect

Bond C-H Stretch in cm-

1

C-1H ~3000

C-2D ~2120
The reduced masses of C-1H and C-2D are different, but their force constants are the same. By
simply doubling the mass of the hydrogen atom, the carbon-hydrogen stretching vibration is
reduced by over 800cm-1.

Table 4. An Example of an electronic Effect

Bond C-H Stretch in cm-1

C-H ~3000

H-C=O ~2750

When a hydrogen is attached to a carbon with a C=O bond, the C-H stretch band position
decrease to ~2750cm-1. These two C-H bonds have the same reduced mass but different force
constants. The oxygen in the second molecule pulls electron density away from the C-H bond
so it makes weaken and reduce the C-H force constant. This cause the C-H stretching
vibration to be reduced by ~250cm-1.

The Origin of Peak Intensities

The different vibrations of the different functional groups in the molecule give rise to bands
of differing intensity. This is because ∂μ∂x∂μ∂x is different for each of these vibrations. For
example, the most intense band in the spectrum of octane shown in Figure 3 is at 2971, 2863
cm-1 and is due to stretching of the C-H bond. One of the weaker bands in the spectrum of
octane is at 726cm-1, and it is due to long-chain methyl rock of the carbon-carbon bonds in
octane. The change in dipole moment with respect to distance for the C-H stretching is
greater than that for the C-C rock vibration, which is why the C-H stretching band is the more
intense than C-C rock vibration.

Another factor that determines the peak intensity in infrared spectra is the concentration of
molecules in the sample. The equation(5) that relates concentration to absorbance is Beer's
law,
 (5)

The absorptivity is the proportionality constant between concentration and absorbance, and is
dependent on (µ/x)2. The absorptivity is an absolute measure of infrared absorbance
intensity for a specific molecule at a specific wavenumber. For pure sample, concentration is
at its maximum, and the peak intensities are true representations of the values of µ/xfor
different vibrations. However, in a mixture, two peaks may have different intensities because
there are molecules present in different concentration.

The Orgins of Peak Widths

In general, the width of infrared bands for solid and liquid samples is determined by the
number of chemical environments which is related to the strength of intermolecular
interactions such as hydrogen bonding. Figure 1. shows hydrogen bond in water molecules
and these water molecules are in different chemical environments. Because the number and
strength of hydrogen bonds differs with chemical environment, the force constant varies and
the wavenumber differs at which these molecules absorb infrared light.

Figure 1. Hydrogen Bonding in water molecules

In any sample where hydrogen bonding occurs, the number and strength of intermolecular
interactions varies greatly within the sample, causing the bands in these samples to be
particularly broad. This is illustrated in the spectra of ethanol(Fig7) and hexanoic
acid(Fig11). When intermolecular interactions are weak, the number of chemical
environments is small, and narrow infrared bands are observed.

The Origin of Group Frequencies

An important observation made by early researchers is that many functional group absorb
infrared radiation at about the same wavenumber, regardless of the structure of the rest of the
molecule. For example, C-H stretching vibrations usually appear between 3200 and 2800cm-
1
and carbonyl(C=O) stretching vibrations usually appear between 1800 and 1600cm-1. This
makes these bands diagnostic markers for the presence of a functional group in a sample.
These types of infrared bands are called group frequencies because they tell us about the
presence or absence of specific functional groups in a sample.

Figure 2. Group frequency and fingerprint regions of the mid-infrared spectrum

The region of the infrared spectrum from 1200 to 700 cm-1 is called the fingerprint region.
This region is notable for the large number of infrared bands that are found there. Many
different vibrations, including C-O, C-C and C-N single bond stretches, C-H bending
vibrations, and some bands due to benzene rings are found in this region. The fingerprint
region is often the most complex and confusing region to interpret, and is usually the last
section of a spectrum to be interpreted. However, the utility of the fingerprint region is that
the many bands there provide a fingerprint for a molecule.
Spectral Interpretation by Application of
Group Frequencies
Organic Compounds
One of the most common application of infrared spectroscopy is to the identification of
organic compounds. The major classes of organic molecules are shown in this
category and also linked on the bottom page for the number of collections of spectral
information regarding organic molecules.

Hydrocarbons

Hydrocarbons compounds contain only C-H and C-C bonds, but there is plenty of
information to be obtained from the infrared spectra arising from C-H stretching and C-H
bending.

In alkanes, which have very few bands, each band in the spectrum can be assigned:

 C–H stretch from 3000–2850 cm-1

 C–H bend or scissoring from 1470-1450 cm-1
 C–H rock, methyl from 1370-1350 cm-1
 C–H rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

Figure 3. shows the IR spectrum of octane. Since most organic compounds have these
features, these C-H vibrations are usually not noted when interpreting a routine IR spectrum.
Note that the change in dipole moment with respect to distance for the C-H stretching is
greater than that for others shown, which is why the C-H stretch band is the more intense.

Figure 3. Infrared Spectrum of Octane

In alkenes compounds, each band in the spectrum can be assigned:

 C=C stretch from 1680-1640 cm-1

 =C–H stretch from 3100-3000 cm-1
 =C–H bend from 1000-650 cm-1

Figure 4. shows the IR spectrum of 1-octene. As alkanes compounds, these bands are not
specific and are generally not noted because they are present in almost all organic molecules.

Figure 4. Infrared Spectrum of 1-Octene

In alkynes, each band in the spectrum can be assigned:

 –C?C– stretch from 2260-2100 cm-1

 –C?C–H: C–H stretch from 3330-3270 cm-1
 –C?C–H: C–H bend from 700-610 cm-1

The spectrum of 1-hexyne, a terminal alkyne, is shown below.

 Figure 5. Infrared Spectrum of 1-Hexyne

In aromatic compounds, each band in the spectrum can be assigned:

 C–H stretch from 3100-3000 cm-1

 overtones, weak, from 2000-1665 cm-1
 C–C stretch (in-ring) from 1600-1585 cm-1
 C–C stretch (in-ring) from 1500-1400 cm-1
 C–H "oop" from 900-675 cm-1

Note that this is at slightly higher frequency than is the –C–H stretch in alkanes. This is a
very useful tool for interpreting IR spectra. Only alkenes and aromatics show a C–H stretch
slightly higher than 3000 cm-1.

Figure 6. shows the spectrum of toluene.

Figure 6. Infrared Spectrum of Toluene

Functional Groups Containing the C-O Bond
Alcohols have IR absorptions associated with both the O-H and the C-O stretching
vibrations.

 O–H stretch, hydrogen bonded 3500-3200 cm-1

 C–O stretch 1260-1050 cm-1 (s)

Figure 7. shows the spectrum of ethanol. Note the very broad, strong band of the O–H stretch.

Figure 7. Infrared Spectrum of Ethanol

The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears:

 C=O stretch - aliphatic ketones 1715 cm-1

- ?, ?-unsaturated ketones 1685-1666 cm-1

Figure 8. shows the spectrum of 2-butanone. This is a saturated ketone, and the C=O band
appears at 1715.
 Figure 8. Infrared Spectrum of 2-Butanone

If a compound is suspected to be an aldehyde, a peak always appears around 2720 cm-

1
which often appears as a shoulder-type peak just to the right of the alkyl C–H stretches.

 H–C=O stretch 2830-2695 cm-1

 C=O stretch:
o aliphatic aldehydes 1740-1720 cm-1
o alpha, beta-unsaturated aldehydes 1710-1685 cm-1

Figure 9. shows the spectrum of butyraldehyde.

Figure 9. Infrared Spectrum of Butyraldehyde

The carbonyl stretch C=O of esters appears:

  C=O stretch
o aliphatic from 1750-1735 cm-1
o ?, ?-unsaturated from 1730-1715 cm-1
 C–O stretch from 1300-1000 cm-1

Figure 10. shows the spectrum of ethyl benzoate.

Figure 10. Infrared Spectrum of Ethyl benzoate

The carbonyl stretch C=O of a carboxylic acid appears as an intense band from 1760-1690
cm-1. The exact position of this broad band depends on whether the carboxylic acid is
saturated or unsaturated, dimerized, or has internal hydrogen bonding.

 O–H stretch from 3300-2500 cm-1

 C=O stretch from 1760-1690 cm-1
 C–O stretch from 1320-1210 cm-1
 O–H bend from 1440-1395 and 950-910 cm-1

Figure 11. shows the spectrum of hexanoic acid.

 Figure 11. Infrared Spectrum of Hexanoic acid

Organic Nitrogen Compounds

 N–O asymmetric stretch from 1550-1475 cm-1
 N–O symmetric stretch from 1360-1290 cm-1
 Figure 12. Infrared Spectrum of Nitomethane

Organic Compounds Containing Halogens

Alkyl halides are compounds that have a C–X bond, where X is a halogen: bromine, chlorine,
fluorene, or iodine.

 C–H wag (-CH2X) from 1300-1150 cm-1

 C–X stretches (general) from 850-515 cm-1
o C–Cl stretch 850-550 cm-1
o C–Br stretch 690-515 cm-1

The spectrum of 1-chloro-2-methylpropane are shown below.

 Figure 13. Infrared Spectrum of 1-chloro-2-methylpropane

For more Infrared spectra Spectral database of organic molecules is introduced to use free
database. Also, the infrared spectroscopy correlation tableis linked on bottom of page to find
other assigned IR peaks.

Inorganic Compounds
Generally, the infrared bands for inorganic materials are broader, fewer in number and appear
at lower wavenumbers than those observed for organic materials. If an inorganic compound
forms covalent bonds within an ion, it can produce a characteristic infrared spectrum.

Main infrared bands of some common inorganic ions:

 CO32- 1450-1410, 880-800cm-1

 SO42- 1130-1080, 680-610cm-1
 NO3- 1410-1340, 860-800cm-1
 PO43- 1100-950cm-1
 SiO42- 1100-900cm-1
 NH4+ 3335-3030, 1485-1390cm-1
 MnO4- 920-890, 850-840cm-1
Diatomic molecules produce one vibration along the chemical bond. Monatomic ligand,
where metal s coordinate with atoms such as halogens, H, N or O, produce characteristic
bands. These bands are summarized in below.

Chracteristic infrared bands of diatomic inorganic molecules: M(metal), X(halogen)

 M-H stretching 2250-1700cm-1

 M-H bending 800-600cm-1
 M-X stretching 750-100cm-1
 M=O stretching 1010-850cm-1
 M=N stretching 1020-875cm-1

The normal modes of vibration of linear and bent triatomic molecules are illustrated and
some common linear and bent triatomic molecules are shown below. Note that some
molecules show two bands for ?1because of Fermi resonance.

Characteristic infrared bands(cm-1) of triatomic inorganic molecules:

Linear Molecules OCO HCN NCS-

ClCN MgCl2

1388, 1286 3311 2053 714, 784 327

667 712 486, 471 380 249

2349
2049 748
2219
842

Bent
Molecules

H2O O3
SnCl 2
 3675 1135 354

1595 716 120

3756 1089 334

Identification
There are a few general rules that can be used
when using a mid-infrared spectrum for the
determination of a molecular structure. The
following is a suggested strategy for spectrum
interpretation:2

1. Look first at the high-wavenumber end of the

spectrum(>1500cm-1) and concentrate initially on the
major bands
2. For each band, 'short-list' the possibilities by using a correlation table
3. Use the lower-wavenumber end of the spectrum for the confirmation or elaboration of
possible structural elements
4. Do not expect to be able to assign every band in the spectrum
5. Keep 'cross-checking' wherever possible.
6. Exploit negative evidence as well as positive evidence
7. Band intensities should be treated with some caution. Under certain circumstances, they
may vary considerably for the same group
8. Take care when using small wavenumber changes. If in solution, some bands are very
'solvent-sensitive'
9. Do not forget to subtract slovent bands if possible

Infrared spectroscopy is used to analyze a wide variety of samples, but it cannot solve every
chemical analysis problem. When used in conjunction with other methods such as mass
spectroscopy, nuclear magnetic resonance, and elemental analysis, infrared spectroscopy
usually makes possible the positive identification of a sample.
Interpreting Infrared Spectra

Table of contents

This chapter will focus on infrared (IR) spectroscopy. The wavelengths found in infrared
radiation are a little longer than those found in visible light. IR spectroscopy is useful for
finding out what kinds of bonds are present in a molecule, and knowing what kinds of bonds
are present is a good start towards knowing what the structure could be.