Summary:

I- Introduction :

P- Purpose of the TP:

Sh- Theoretical part:

IV- Experimental part :

V-Results and discussion:

VI- Conclusion :

VIIBibliographic references:
I- Introduction :
Infrared spectroscopy (sometimes referred to as IR spectroscopy) is
a spectroscopy class that deals with the infrared region of the spectrum
electromagnetic. It covers a wide range of techniques, the most
commune is a type of spectroscopy ofabsorptionAs with all the
spectroscopy techniques, it can be used for identification of
composed or to determine the composition of asampleThe tables of
correlation ofinfrared spectroscopyare largely present in the
literaturescientific.
The infrared part of the electromagnetic spectrum is divided into three regions:
the near, mid, and far infrared, named in relation to the
visible spectrum. The far infrared, ranging approximately from 400 to 10 cm-
1 (1000–30 μm), medium of the microwave region, has low energy and can
to be used for rotational spectroscopy. The mid-infrared, ranging
approximately from 4000 to 400 cm-1 (30–1.4 μm) can be used for
study the fundamental vibrations and the associated vibrational structure.
near infrared, more energetic, ranging approximately from 14000 to 4000
cm-1 (1.4–0.8 μm) can excite harmonic vibrations. The denominations
and classifications of these sub-regions are essentially conventions. They
are not based on strict divisions or on molecular properties
or exact electromagnetic.
Infrared has all the fundamental properties of light:
propagation, réflexion, réfraction, interférences, diffraction, diffusion,
polarization, etc. IR spectroscopy covers a wide technical range,
most common being a type of adsorption spectroscopy. As with all
spectroscopy techniques, it can be used for identification of
compounds or to determine the composition of a sample. IR allows
the study of molecular vibrations. Among these are the vibrations
elongations are particularly interesting during an elucidation
structural. There are other vibrations called deformation vibrations for a
global study of vibrations associated with different functions of chemistry
organic. It addresses the main functions of organic chemistry:
Hydrocarbon compounds: alkanes, alkenes, alkynes, and aromatic...
with the study of the vibrations of the groups C-H, -CH2-, -CH3, -C≡C-,
⟩C=C⟨.
 Oxygenated compounds: alcohols, ethers, aldehydes, ketones, acids, esters,
anhydrides, lactones.... With the study of the vibrations of the groups -
OH, -OR,⟩C=O.
Nitrogen compounds: amines, amides, with the study of vibrations of
N-H groups,⟩C=O.

P- Purpose of the TP:

Study of the influence of the molecular environment on the grouping

anhydride (study of symmetrical and asymmetrical vibrations).
Familiarize with IR and save the spectrum.

Sh- Theoretical part:

To determine the expanded formula of a molecule, one can use
various methods:

Chemical methods: we use test reactions that allow us to

highlight the presence of characteristic groups. This method
does not allow to determine the place of the groups in the chain
carbonated.

Physical methods: most often spectroscopic, which have the advantage

to be quick, to require only a few mg of products. But they require
an expensive device.
Spectroscopic techniques allow for the determination of structures of
molecules. Apart from mass spectrometry, they rely on interaction
between matter and electromagnetic radiation. Non-destructive, they
allow a priori the recovery of the sample.

1) Infrared spectroscopy:
It is a spectroscopy based on the absorption of infrared radiation.
Energy transitions occur here between the rotational energy levels.
of molecules or between their vibrational energy levels.
 The analysis of absorbed radiation allows for the identification of transitions between
energy levels and deduce information about the structure of the
molecule the energies involved are primarily vibrational energies
(in the near infrared) but also of rotation (far infrared).

2) Scope of application:
The domain of application of infrared is:
Near infrared: (0.7 μm < λ < 3 μm).
Mid-infrared: (3 μm < λ < 25 μm).
Far infrared: beyond 25 μm.

The transitions between rotational levels appear in the far IR.

transitions between vibrational levels occur from 10,000 to 500 cm-1We
We will focus our study on vibrational transitions.

It is observed that they require more energy than the transitions.

rotational. Also, the excitation light will cause, for each
vibrational transition, a multitude of rotational transitions, which will
give the peak of vibrational transition the shape of an absorption band
 Molecular vibration:

The molecule, a non-rigid assembly of atoms, resembles a system of

balls (the atoms), linked to each other by springs of constant
stiffness more or less great (the connections) whose vibrations appear at some
determined frequencies0

For a covalent bond A-B, modeled by two balls of mass mAand

mBlinked by a spring with a stiffness constant, the frequency Ʋ0of vibration
check:

1
Ʋ 0= 2 π √ K/ μ → µ=mA. mB/mA+ mB
µ: the reduced mass of the system.

Quand un rayonnement infrarouge de l’une des fréquences de vibrationƲ0of

the molecule is struck, there is resonance; the amplitude of the vibration increases and
energy is absorbed.

The IR absorption spectrum of the molecule thus has bands

of absorption, quite broad, which correspond to the transitions between the levels
vibrational (and rotational) energy.

4) The modes of vibrations:

One can consider that there are two types of
fundamental vibrations in the molecule:
Valence or elongation vibrations: are
vibrations between two given atoms during
of which the interatomic distance varies along the axis
of the connection. (Symmetrical and asymmetrical)

Angular deformation vibrations are

vibrations during which the angle formed by
two contiguous connections vary. We distinguish: the
deformations vibrations in the planes and the vibrations
out-of-plane deformation.
 Figure 04: elongation and deformation vibrations

5) Types of spectrometers:

There are two main types of devices. Their differences lie in

essentially in the wavelength selector system.

5-1- Dispersive spectrometers:

The first infrared spectrometers are of the dispersive type. These devices
are designed according to the schematic principle shown in figure 6:

Figure 5: Principle diagram of a dispersive IR spectrometer

 These instruments separate the frequencies of the energy emitted from the
infrared source using a prism (in NaCl usable up to 650 cm-1or
in KBr usable up to 400 cm-1) or diffraction networks.

The detector measures the amount of energy for each frequency that passes through.
through the sample. This results in a spectrum which is the plot of the intensity I =
f(ν).

The disadvantages of these devices are:

the relative slowness of the measurements (given that the instrument measures each
individually, the recording of a sample takes from 10 to 15
minutes)
the relative insensitivity (detection requires a reasonable amount of
product for a usable analysis).
mechanical complexity.

5-2- Fourier Transform Spectrometers (FT-IR):

An FT-IR spectrometer essentially consists of four parts:

A light source
The interferometer: The Michelson interferometer is formed by a blade
semi-transparent separator that divides the beam from the source into two
beams, one reflected towards a fixed mirror, the other transmitted towards a mirror
mobile. The interferometer produces a unique signal containing all the
required information to produce a spectrum. It can be measured very
quickly
A sample compartment
• A detector: to detect and calculate the difference between absorption and the beam
of reference and that coming from the sample.
The analog to digital converter: converting the intensity signal into
function of mirror displacement I=f(δ) to a signal of intensity as a function
the wave number I = f(ν) is obtained using a mathematical processing
called Fourier transform.
Figure 06: schematic diagram of the principle of Fourier spectroscopy analysis
(FT-IR)

6) Techniques for Sample Examination in FT-IR Spectroscopy

The choice of sampling technique depends on the nature of

the sample.
Several methods have been developed for the characterization of samples.
different physical states by infrared spectroscopy using
specific accessories.

6-1- Transmission processes:

The infrared beam passes through the sample and the energy coming from
the latter is measured. The transmission T is defined as the fraction
of light energy passing through the sample.

T = I/I0
 Figure 7: Principle of transmission

6-2 - Processes by reflection:

When a beam of light arrives at the interface of a second medium whose

the refractive index is greater, it undergoes according to the angle of incidence, either a
total reflection like a mirror, or a weakened reflection.
The sample absorbs a part of these radiations. Several techniques
exploit this principle and allow the observation of all kinds of samples. We
distinguishes specular reflection, attenuated total reflection, and reflection
diffuse.

7) Attenuated Total Reflection ATR:

The principle of ATR devices is to subject the optical beam

several reflections at the interface between the sample and a crystal
parallelepiped, transparent in IR but with a high refractive index n2 (ZnSe,
TlBr, AgCl, diamond…) and in most cases, higher than that of
the sample (n1). In the first approximation, according to Descartes' law,
initial IR beam of intensity I(source) passes through the crystal and undergoes reflection
total to the crystal interface sample then directed to the detector.

In reality, the phenomenon is disturbed by the existence of a progressive wave

called evanescent. It penetrates a few micrometers into
the sample in direct contact with the crystal and may be absorbed:
A part of the energy is retained and total reflection is dampened.

The intensity of the reflected light IRis measured by a detector of

reflection. We call I0the intensity reflected by a non-absorbing material taken
as a reference. The reflectance R is: R=IR/I0.
 Figure 08: Principle of attenuated total reflection (ATR)

The advantages of the ATIR:

minimum sample preparation

cleaning of the accessory simple and quick,
possibility to study the samples directly in their natural state (without
preparatory work,
- very reproducible technique: quantitative analysis, provided that one does not
claim very important sensitivities,
ATR cells capable of working at temperature or on products
corrosives (acids, peroxides...)

8) The different zones of the spectrum in Infrared

Generally speaking, the masses of the atoms studied in organic chemistry (C,
N, O... ) are almost identical, similarly, the bond energies are
relatively similar, which leads to identifying different areas of the spectrum
depending on the observed absorption:
 Figure 9: The different zones of the infrared spectrum
An infrared spectrum is traditionally presented in transmittance (fraction
the transmitted intensity compared to the incident intensity) expressed in
percentage and the x-axis as a function of the wave number (inverse of the
wavelength), on an axis directed to the left.
The Beer-Lambert law is verified in infrared, making it a method
of quantitative analysis, it should be remembered that this law uses the
absorbances (logarithm of transmittance) in its application.
A more detailed analysis then allows us to identify the different functions
present.

The elongation vibrations of X-H bonds:

According to Hooke's law, two parameters must be considered for the study
vibrations of the X-H bond elongation. The first is the atom X (and more
particularly its mass), we will distinguish the case of oxygen atoms,
of nitrogen and carbon, the latter being the most commonly encountered in
organic chemistry.
The stretching vibration of O-H and N-H bonds:

In the gas phase, the elongation vibrations of the O-H and N-H bonds occur
presented in the form of a thin band, respectively between 3590 and 3650
cm-1 and between 3300 and 3500 cm-1. In solution or in pure liquid, the hydrogens
are engaged in H bonds, which has the effect, on one hand, of weakening the
liaison (decrease in the number of waves) and on the other hand to cause a widening
stripes due to solvation effect.
For a long time, infrared has allowed the quantification of the strength of H bonds.
les nombres d'onde de vibration dépendant largement de l'atome avec lequel le
bridge was committed:

Ï?v(O-H) = 2500 to 3200 cm-1

X = O or NR (strong intensity) Thus, in concentrated solution or

in pure liquid, alcohols have
Ï?v(O-H) = 3200 to 3600 cm-1
tendency to present a wide
X = OR or NR2 variable intensity band OH between 3200 and 3600 cm-
1 while the acids
carboxylics will present a much broader band between 2500 and
3200 cm-1.
The hydrogens of nitrogen atoms have less tendency to form bonds
Compared to their oxygenated analogues, amines do not present such
displacement. Infrared, however, allows us to distinguish between different classes.
of amines, since the NH2 group of a primary amine will exhibit two bands.
of the N-H vibration, corresponding to the symmetric and antisymmetric modes,
whereas a secondary amine will show only one intensity band
average.

The stretching vibrations of C-H bonds:

The stretching vibration bands of C-H bonds extend over a range

ranging from 2850 to 3100 cm-1. One of the main interests is that the vibrations of
C-H bonds largely depend on the carbon atom bearing the hydrogen:
the hydrogens bonded to a saturated carbon exhibit their vibration bands in
below 3000 cm-1, whereas in the case of an unsaturated carbon, these bands are
above 3000 cm-1.

ν(C-H) = 2850 to 2960 cm-1

Ï?v(C-H) = 3000 to 3100 cm-

1

Ï?v(C-H) = 3300 cm-1

The vibration of the elongation of the C=O bond:

The stretching vibration of the C=O bond absorbs between 1650 and 1800 cm-1.
region little solicited by other absorptions, and is therefore easily
recognizable. Many pieces of information can be obtained from the
position of the absorption band.

Carbonyl compounds:

Aldehydes have a characteristic absorption between 1720 and 1740 cm-

1, the ketones between 1705 and 1725 cm-1. As soon as the carbonyl is conjugated,
these values are lowered from 15 to 40 cm-1.
The position of the absorption band is also heavily influenced by the tension.
of the cycle, which makes it easy to characterize the size of a (stretched) cycle
containing a carbonyl.

Ï?v(C=O) = 1685 to 1705 cm-1

Ï?v(C=O) = 1740 to 1750 cm-

1

Ï?v(C=O) = 1780 cm-1

Furthermore, the hydrogen bond acceptor carbonyl sees its absorption frequency
decrease from 40 to 60 cm-1.

Derivatives of carboxylic acids:

In RC(=O)X systems, the more electronegative X is, the higher the frequency
absorption is increased.

1800 to 1850 cm-1

 1740 to 1790 cm-1

1790 to 1815 cm-

1

1735 to 1750 cm
1

1700 to 1725 cm
1

1630 to 1700 cm
1

These bands are largely influenced by the presence of H bonds.

Deformation vibrations in aromatic compounds:

Deformation vibrations generally have a higher absorption frequency.
low and a lower intensity than the elongation vibrations, which leads to
the bands in the fingerprint area and makes their detection and analysis
delicate.
However, in the case of aromatic compounds, the deformation bands
out of the plan, situated between 680 and 900 cm-1, are intense and allow for
determine the different substitutions of the aromatic cycle.

735 to 770 cm-1

5H neighbors (monosubstituted) 685 to 710 cm-1
strong intensity

740 to 760 cm-1

4H neighbors (o-disubstituted)
strong intensity

3H neighbors (m-disubstituted, 1,2,3- 770 to 800 cm-1

trisubstituted strong intensity

800 to 840 cm-1

2H neighbors (p-disubstituted...)
strong intensity
 800 to 900 cm-1
H isolated (p-disubstituted...) low intensity (often not
visible

After studying the theory of infrared spectroscopy, then seeing some

spectral analysis elements, we propose to study the different
techniques that allow the acquisition of these spectra.

Preparation of an Infrared sample:

Depending on the nature of the sample, solid or liquid, the techniques differ. A
solid will be crushed in the presence of potassium bromide (which is transparent)
up to 400 cm-1) then compressed under reduced pressure to form a thin
tablet. Another technique consists of dispersing the solid in a paraffin (the
nujol) and to deposit the suspension on a sodium chloride tablet.
monocrystalline (transparent up to 625 cm-1).
A liquid will be placed between two sodium chloride pellets.
monocrystalline compressed, in order to obtain a thin film, or placed in a
tank whose windows will be made of sodium chloride monocrystals or
calcium fluoride (which has the advantage of not being altered by water). In the case of
pure liquids, the thickness of the tank is often too great to obtain
a specter of satisfactory quality.
Another technique, applicable to both liquids and solids,
consists of preparing a diluted solution of the product in a solvent, and then studying
this solution in the previously described tanks. It should be noted that all the
solvents have infrared absorption bands and it is necessary
to compensate his bands with a reference. The compensation not being
always perfect, the solvents used for the solutions are chosen so as not to
present absorption bands in particularly interesting areas of
tetrachloride of carbon,
chloroform and carbon disulfide (CS2).
Finally, one last technique (ATR, Attenuated Total Reflection), which is gaining
increasingly popular, involves using the properties of waves
electromagnetic at a dioptre formed by a crystal of germanium or selenide
of zinc and the product to be analyzed, under total reflection conditions. In these
conditions, an evanescent wave is created in the product part of the diopter on
a thin layer of skin, which is partially absorbed by the product. The spectrum
obtained after calculation allows for conducting to the classical spectrum in transmittance.
 Figure 10: ATR Device (germanium crystal)

9) Qualitative and quantitative analyses:

Qualitative analysis involves making an attempt to identify the

composed analyzed by the comparison method. But this step is always
difficult due to the complexity of the spectrum.
However, the attempt to attribute most of the characteristic bands of the
spectre is sometimes very affordable especially if the molecular formula of the compound is
known.

We make a choice of the band that will be used for the quantitative analysis.
Typically, our choice is made on the most intense, the most resolute band and
the finest. The accuracy of absorbance measurements and the possibilities of
spectrum processing has favored quantitative analysis by infrared.

The method has become widely used both because it is easy in the
IR means to identify specific bands in a mixture spectrum.
composed to be dosed and because we have statistical processing methods
effective for the near IR.

Quantitative analysis is done by applying Beer-Lambert laws:

A=Ɛ l C
 10) Advantages of FT-IR spectroscopy:

Speed: Simultaneous measurement of all frequencies takes a few seconds.

Reproducibility and reliability.
High spectral resolution.
Mechanical simplicity: the only moving part of the instrument is the mirror
mobile.

11) Disadvantages of FT-IR spectroscopy:

Milling and pressing can alter the physico-chemical nature of

the sample, while certain regions of the spectrum may be masked by
the absorption bands of the oil.
difficult for highly absorbent products or those that cannot be ground.
Do not indicate the location of the molecule.
Very sensitive to water and CO2

12) The application of IR spectroscopy:

Infrared spectroscopy is very common in academic research.

and the industry as a simple and safe technique for measurement, control of
quality and dynamic measurement. It is, for example, used inmedicine
legalfor criminal or civil cases for the characterization of thedegradation
polymericIt is undoubtedly the technique ofapplied spectroscopythe most
used.

Infrared spectroscopy is a proven technique in both chemistry

organic and inorganic chemistry. Thus it can be used in surface analysis
in the microelectronics industry for semiconductors like the
silicon, l'gallium arsenide, thezinc selenide, amorphous silicon, the
silicon nitride, etc.

Experimental device:

1) Shimadzu FT-IR 8400s Spectrometer:

Fourier transform infrared spectroscopy is excellent
single spindle device allowed to define the functional groups
in molecules.
 Figure 11: Shimadzu FT-IR 8400s spectrophotometer

2) the sample holders:

-sample holders (for liquid samples): it consists of blades of
KBr (it needs to be rinsed well with DMF) which are located on two supports and they
are well fixed.

-sample holders (for solid sample): are plates or

small wheels where we place a disc to fix it to the device's support.
 3) The press: it is a tool for applying pressure on the matrix.
to form the tablet manually

4-The matrix:
In IR spectroscopy, the matrix is considered as a mold of
preparation of the tablet.

5-The mortar: where a solid product is crushed and turned into powder.
 IV- Experimental part:
1- Materials and products:

a) Materials: the materials and instruments used are:

Materials: Pasteur pipette, mortar and pestle, spatula, beaker, tank.
Instruments: hydraulic press, removable cell, tablet molds
Names Dangers Chemical formulas

Maleic anhydride
H302, H314,
H317, H334

Succinic anhydride R36-37

H226, H302
Acetic anhydride H314, H332

Glutamic anhydride H302, H315, H318

Potassium bromide (bromide R36/37/38 KBr

of
potassium

b) Products :
 2- Soft methods:
Preparation of the KBr pellet:

We weighed some milligrams of dispersant (KBr) in a mortar and ground it very finely.
Finally to remove the water contained in the KBr.
It is placed in a mold subjected to a pressure of 8 tons, and we
attend 2 to 5 minutes then we separate the two metal tablets.
to obtain the transparent solid pellet.
We placed this disk in the holder and then the ring for the
keep in place, and analyze the spectrum.

Preparation of glutaric anhydride tablet:

We weighed 0.5 to 2 mg of glutaric anhydride and mixed it, the mixture

is ground very finely in a mortar.
With 100 mg of KBr. The mixture is placed in a tablet press.
We separated the two metal discs to obtain the disc of
solid transparent.
We placed this pellet in the holder and analyzed the spectrum.
In the same way, we obtain the spectra of the anhydride.

Preparation of a liquid solution:

Acetic anhydride: succinic and maleic.

We rinse the two plates with CCl4 and we fix one on the cell, we
pour a few drops of acetic anhydride on the fixed plate, then we
close our cell and place it in the sample holder then in the
spectrometer for analyzing and tracing the spectrum

Make the spectrum of 4 anhydrides:

Solution1: acetic anhydride

Solution 2: glutaric anhydride
Succinic anhydride
Solution4: maleic anhydride

The solid dispersant KBr

We turn on the device and the computer:
IR software is:
 To start the analysis:

We're waiting for the green light

2. background
3. measure → polystrene
4. measurement (simple sear)
5. calculate → add peak

to print and save:

1. print preview (choose type of impression)

2. environment graph preference (we can change the color of the graph)
3. for soothing the graph:
3.1. manipulation
3.2. smoothing
3.3. calculation
3.4. calculate
4. print

V- Results and discussion:

Results:
The following spectra were obtained:
Discussion and interpretations:
Interpretation of specters:

1- Succinic anhydride:

-C=O: stretching band ν (C=O) at 1783.07 cmˉ¹

Strong.
-C-O(Ester): 2 elongation ν (CO):
1-band at 1057.88 Cm⁻¹
2-band at 1308.61 cm⁻¹
-C-O(Ether): elongation ν (C-O) at 1202.53
(my)
-CH: ₂ elongation ν (C-H) at 2930.63 cm ⁻¹ (average).
A deformation band δ (C-H) at 1419.51 cm⁻¹ (average).

2- Maleic anhydride :

-C=O : 2 elongation ν (C=O) :

1772.58 Cmˉ¹(strong) symmetrical.
-1
1850 Cm (strong) asymmetrical.
-C=C: elongation ν (C=C) at 1751.36 cm⁻¹ (weak).
-C-O (Ester): 2 elongations ν (C-O)
band at 1056.99 cm⁻¹ (strong).
*band at 1288.45 cm⁻¹ (avg).
-C=O (ketone): elongation ν (C=O): at 1735.93 mˉ¹ (weak).
-CH ₂: elongation ν (C-H) : at 3100 Cmˉ¹ asymmetric (avg).
deformation δ(C-H) at 1400 cm⁻¹ (weak).
3- Glutamic anhydride:

-C=O: elongation ν (C=O) at 1754.14 cmˉ¹ (strong).

-CH : 2 elongation ν (C-H) :
band at 2921.96 cm-1(weak).
band at 3041.53 cm⁻¹ (weak).
2 deformations δ (C-H):
*1411.80 Cmˉ¹(faible) et1219.89 Cmˉ¹(moy).

4- Acetic anhydride:
 -C=O : elongation ν (C=O) at 1827.43 cmˉ¹ (weak).
-C-O(Ester) : 2 elongation ν (C-O) :
1-band at 1122.49 cm⁻¹ (strong).
2-band at 1224.71 Cm⁻¹ (weak).
-C-O (Ether): elongation ν (C-O) at 1045.35 cm⁻¹ (strong).
-C-H: elongation ν (C-H) at 1752.21 cm⁻¹ (weak).
2 deformations δ (C-H):
1- à1429.15 Cmˉ¹asymmetric (low).
at 1368.40 cmˉ¹ symmetrical (strong).

VI- Conclusion :
This lab allowed us to conclude that IR spectroscopy is a method of
rapid and sensitive characterization of most existing molecules.

The analysis of these different products has allowed us to study the various peaks.
of each product and to differentiate them. And that when we have a tablet
thick we can have a good spectrum in the case of solids, in the case of
liquids a well-diluted product equals a good spectrum.
From the results obtained, we can say that we have successfully achieved our objective of
this lab.

VII- bibliographic references :

[Link]
[Link]
[Link]
spectroscopies/introduction-to-infrared-spectroscopy-ir
[Link];
[Link] ⟩wiki⟩Infrared spectroscopy
[Link]⟩Infrared spectroscopy
nces [modifier | edit the code]
W.S. Lau, Infrared characterization for microelectronics, World
Scientific, 1999