Contents

Introduction Electromagnetic Spectrum Origin of Electronic Spectra

Emission Spectra Absorption Spectra

3 4 5
5 6

Laws of Light Absorbance

Lambert's Law Beer's Law

7
7 9

Infrared Spectroscopy Modes of Vibration

Stretching Vibrations Bending Vibrations

11 13
14 14

Infrared Region Infrared Instrumentation

General parts of IR spectrometer Sampling

15 16
16 17

Principle of IR Spectrometer IR Spectra of Hydrogen Characteristic IR Absorption of Groups

19 20 22

Factors Affecting Vibrational Frequencies 24

Applications of IR Spectroscopy

26

Introduction
Spectroscopy is that branch of science which deals with the determination of a substance of a compound through the interaction of electromagnetic radiation with the matter.

Previously used classical methods of analysis are:

i) Melting and boiling point ii) Optical rotation iii) Solubility iv) Functional group analysis

Advantages of Spectroscopy Methods over Classical Methods of Analysis:

i) Spectroscopic methods take much less time. ii) For spectroscopic analysis, only a very small amount of the substance is sufficient. iii) Spectroscopic methods are comparatively more reliable in establishing the structure and identity of a compound.

iv) The substance remains generally unaffected or unchanged during spectroscopic examination and can be reused for other tests, if required.

Electromagnetic Spectrum
Light is an electromagnetic radiation, having visible, ultraviolet, infrared, X-rays, radio and radar waves. All these waves have the same velocity i.e. 3x108 m/s (speed of light).

When a beam of electromagnetic radiation is passed through a substance, the radiation can be either absorbed or transmitted, depending upon its frequency and the structure of the molecule it encounters. Electromagnetic radiation is energy, so when a molecule absorbs radiation, it gains energy. The higher the frequency, the greater is the gain in energy.

The gain in energy and frequency of the radiation are connected by the following relation: E = hv As E and v are directly related, radiation with higher frequency leads to a greater gain in energy. In other words, the shorter the wavelength of a radiation, the more energetic it is.

Origin of Electronic Spectra

Electronic spectra can be classified into two types:

i) Emission spectra ii) Absorption spectra

i) Emission Spectra:

When a substance is subjected to a large amount of heat or to an electric discharge, its atoms or molecules absorb energy and are excited. When these excited species return to their ground state, they may emit radiations which, on passing through a prism, give rise to a spectrum, known as Emission Spectrum.

If such a spectrum is recorded on a photographic plate, the atoms in it appear as bright lines in a dark background and molecules appear as band.

Ee

hv Eg

ii) Absorption Spectra:

Absorption spectrum results when an electron in an atom or molecule undergoes a transition from the lower energy level to a higher one with the absorption if a photon of energy hv, provided hv is exactly equal to the energy difference (E = EeEg) between the two levels. Ee

hv Eg

Types of Absorption Spectra

The initial energy of a molecule may be considered to be sum of: Electronic energy Vibrational energy Rotational energy Translational energy

i.e.

Einternal = Eelect + Evib + Erot + Etrans

Translational energy is not quantized so it is negligibly small and we can neglect it, hence

Einternal = Eelect + Evib + Erot

i) Ultraviolet Spectroscopy (UV) ii) Visible Spectroscopy iii) Infrared Spectroscopy (IR) iv) Nuclear Magnetic Resonance (NMR) Spectra

Laws of Light Absorbance

The absorbance of radiation is governed by two empirical laws:

i) Lamberts Law ii) Beers Law

Lambert's Law: When a monochromatic radiation is passed through a solution, the decrease in intensity of radiation, with the thickness of the

solution, is directly proportional to the intensity of incident radiation.

Let the intensity of incident radiation = I

Rate of decrease in intensity of incident radiation= - dI dx

According to Lambert's Law,

- dI dx

- dI = dx

KI

(K: proportionality constant)

- dI = I

Kdx

On integration between the limits

I = Io to I x = 0 to L

We get,

log ( I / Io ) = - KL

2.303 log ( I / Io ) = - KL

log ( I / Io ) = - KL / 2.303

log ( I / Io ) = A (Absorbance or optical density) KL / 2.303 = (Absorption Coefficient)

A=

Beer's Law: When a monochromatic radiation is passed through a solution, the decrease in intensity of radiation, with the thickness of the solution, is directly proportional to the intensity of incident radiation as well as concentration of the solution.

Let the intensity of incident radiation = I

Concentration of the solution = C molar

Rate of decrease in intensity of incident radiation= - dI dx

According to Beer's Law,

- dI dx

CI

- dI = dx

KCI (K: proportionality constant)

- dI = I

KCdx

On integration between the limits

I = Io to I x = 0 to L

We get,

log ( I / Io ) = - KCL

2.303 log ( I / Io ) = - KCL

log ( I / Io ) = - KCL / 2.303

log ( I / Io ) = A (Absorbance or optical density) KCL / 2.303 = (Absorption Coefficient)

A=

CL

Infrared Spectroscopy
IR spectroscopy is one of the most powerful analytical techniques which give us the possibility of identification of a compound. Radiations in the infrared region are not energetic enough to cause electronic excitations in most organic molecules. Although, infrared radiations are weak, it supplies

sufficient energy for bonds in the molecules to vibrate by stretching or bending.

For a molecule to be IR active, it should fulfil the following necessary conditions:

i) The frequency of the vibration must satisfy the equation E = hv

ii) The intensity of absorption must be proportional to square of the rate of change of dipole.

iii) The natural frequency of vibration of the molecule must be equal to the frequency of incident radiation.

iv) Change in vibration must involve changes in the dipole moment of the molecule.

An infrared spectrum is a highly characteristics property of an organic compound and can be used both to establish the identity of two compounds and to reveal the structure of a new compound.

A diatomic molecule has only one vibrational mode and hence it yields a rather simple system.

For a polyatomic molecule, several vibrational modes are possible therefore a complicated IR spectrum is obtained for it.

Modes of Vibration
Normal modes of vibrational are of two types:

i) Stretching Vibrations (a) Symmetric Stretching (b) Asymmetric Stretching

ii) Bending Vibrations (a) Scissoring (b) Rocking (c) Wagging (d) Twisting

Stretching Vibrations
In this type of vibrations, the distance between two atoms increases or decreases but the atoms remain in same bond axis.

Stretching vibrations are of two types:

(a) Symmetric Stretching: When the stretching and compressing occurs in a symmetric way, it is called symmetric stretching.

(b) Asymmetric Stretching: When one bond is compressed and the other is stretching than it is known as asymmetric stretching.

Bending Vibrations
Such type of vibrations may consist of a change in bond angle between bonds with a common atom.

Bending vibrations are of four types:

(a) Scissoring: In it two atoms approach each other.

(b) Rocking: It involves the movement of atoms in same direction.

(c) Wagging: The atoms move up and below the plane with respect to central atom.

(d) Twisting: It involves the movement of one atom up and the other atom down the plane with respect to central atom.

Infrared Region
IR region is studied in two parts:

i) Functional-group region The bands in this region are particularly useful in identification of the type of functional groups present in the organic molecule. This region lies in between 4000cm-1 to 1300cm-1.

ii) Fingerprint region The area from 1300cm-1 to 687cm-1 is called the fingerprint region. The IR spectrum of an unknown substance compared with spectra of possible substance. Fingerprint region is associated with complex vibrational and rotational energy changes and is characteristic of the molecule as a whole.

Infrared Instrumentation
The instrument used for recording infrared spectra is called infrared spectrometer or spectrophotometer. Most of the instruments have a range of 2 to 15 (4000 to 667 cm-1)

The general parts of IR spectrometer and their functions are as follows:

i) Radiation Source: The source of IR radiation is primarily an incandescent material, which has characteristics of a black body radiator. The tungsten filament lamp is the usual source of near IR region. It is maintained at red hot by means of electric current. The function of radiation source is to provide IR energy from 4000 to 400 cm-1.

ii) Infrared Monochromator: Prisms and gratings are generally used as monochromators. The most common prism material which is used is NaCl (rock salt) for the range 4000 to 650 cm-1. KBr and CsI are commonly used.

iii) Cell Compartment: It is the portion where the cell with the sample under examination is placed. Cell compartment are usually made of rock salt (NaCl).

Sampling
It is important that substances are sampled suitably for infrared spectral studies.

i) Gaseous substance: They are examined as such in the apparatus.

ii) Liquid substance:

They are examined by placing a thin film between two rock salt plates of a liquid cell. A drop of the liquid is put on a rock salt plate and the other plate is put on it so that the liquid forms a thin film between the two plates.

iii) Solid substance: They are examined in the solid form of a potassium bromide disc or a solution (Nujol Mull) in a suitable solvent.

(a) KBr pellet: The solid is ground with 10-100 times its bulk of pure KBr and the mixture so obtained is passed into a disc using a special mould through a hydraulic press. The pellet must be transparent.

(b) Nujol mull: Nujol is highly purified liquid fraction petroleum known as liquid paraffin. The solid substance is finally mixed with nujol and a paste of it is taken for analysis.

(c) The given compound is dissolved to give 1-5% solution in CCl4, carbon disulphide (CS2) and chloroform.

Principle of IR Spectrometer

First of all, a beam of IR rays from the source 'S' is allowed to pass by means of lens 'L' through a narrow slit 'T'.

This beam is focussed by means of a mirror 'M' on the grating 'G', which is provided with a rotating device.

The radiations of a desired wavelength emerge from 'G'. Such radiations are allowed to pass through a cell 'B' (which is having the solution to be examined) and from 'B' it passes into detector-cum-indicator. The intensity of the incident radiation 'I' is recorded. The cell 'B' is then replaced by a cell containing pure solvent 'C' and again the intensity of radiation 'Io' is recorded as before.

If I and Io represent the intensity of radiation when the radiation passes through the solution and intensity of same radiation when it passes through the solvent then transmittance is determined at different wavelength and thus IR spectrum obtained.

IR Spectra of Hydrogen
As hydrocarbons are made up of carbon and hydrogen only, and thus in IR spectrum of these compounds, we shall see absorption bands due to vibrations of carbon-hydrogen and carbon-carbon bonds.

Hydrocarbons may be saturated (alkanes), unsaturated (alkenes), cyclic or aromatic. The characteristic bonds due to stretching and bending vibrations in hydrocarbon are as follows.

C-H Stretching Vibrations

Alkanes Alkenes & Aromatics

2800 3000 cm-1 3000 3100 cm-1

C-H Bending Vibrations Bending occurs at lower frequency than stretching vibrations.

Alkanes Alkenes Methylene gp.

CH

1340 cm-1

CH2

1485 1445 cm-1

Alkanes Methyl gp. CH3 CH3 Isopropyl gp. C CH3 1385 and 1370 cm-1 1380 1370 cm-1

CH3 Tertiary butyl gp. C CH3 CH3 1370 and 1395 cm-1

Characteristic IR Absorption of Groups

Group Frequency

Alkyl s CH stretching Isopropyl Tert.butyl gp. Alkanes Alkenes Aromatic CH stretching C=C stretching CH bending 3100 - 3000 cm-1 1600 - 1500 cm-1 900 - 700 cm-1 2853 - 2962 cm-1 1385 - 1370 cm-1 1370 - 1395 cm-1 2800 - 3000 cm-1 3000 - 3100 cm-1

C=C C=N C=C C=O

2100 - 2260 cm-1 2220 - 2280 cm-1 1620 - 1680 cm-1 1630 - 1780 cm-1

Group

Frequency

Alcohols, Phenols and Carboxylic Acids OH stretching Alcohols Phenols Carboxylic Acids 3590 - 3650 cm-1 3200 - 3550 cm-1 2500 - 3000 cm-1

Aldehydes, Ketones, Esters and Carboxylic Acids C=O stretching Aldehydes Ketones Esters Carboxylic Acids Amides 1630 - 1780 cm-1 1690 - 1740 cm-1 1680 - 1750 cm-1 1710 - 1780 cm-1 1630 - 1690 cm-1

Q1. How can you distinguish between the C-H stretching absorption of an alkane and aromatic compound? A. In case of aromatic compound, C-H stretching is above 3000 cm-1 while alkane, C-H stretching is just below 3000 cm-1.

Q2. Methane does not absorb IR energy. Why? A. The four Hydrogen atoms in methane vibrate symmetrically. Since there is no change n dipole moment during vibration so methane does not absorb IR energy.

Q3. Distinguish between ethyl alcohol and dimethyl ether on the basis of IR spectroscopy? A. Ethyl alcohol will show strong and broad O-H stretching band at 3200 - 3600 cm-1 region. Dimethyl ether has no O-H group, thus it will not show this band.

Factors Influencing Vibrational Frequencies

i) Physical State:

Variations in the physical state influence the IR frequencies by means of association effects. In the vapour state, a substance usually absorbs at higher frequency as compared to liquid or solid state. For example cyclopentanone shows the carbonyl absorption band in the vapour phase at 1772 cm-1 and in liquid phase at 1746 cm-1.

ii) Effect of Solvent: Change of solvent also shifts the IR band. The more volatile the solvent, the less will be its frequency of absorption. Hexane > Chloroform > Ethyl Alcohol
1726 cm-1 1713 cm-1 1709 cm-1

iii) Coupled Vibration and Fermi Resonance: Vibrational coupling takes place between two bands through a common atom, vibrating with similar frequencies. When the coupling is between two fundamental bands (Strong bands), it is called coupling vibrations. And when coupling is between fundamental and overtone, it is called Fermi-resonance.

iv) Electronic Effects: Under the influence of electronic effects (inductive effect, mesomeric effect) force constant or bond strength changes and the absorption shifts from the normal value.

For example, the absorption of carbonyl group in the following compounds occurs at

Compound Absorption

HCHO 1750

CH3CHO 1745

CH3COCH3 1715

The introduction of -CH3 group causes +I effect in CH3CHO and CH3COCH3 which results in lengthening or weakening of the bond and hence force constant is lowered and wave number of absorption decreases.

v) Hydrogen Bonding: It brings about downward frequency shifts. Stronger the Hbonding, greater are the absorption shifts towards lower wave number than normal value. Inter and intra-molecular H-bonding can be easily distinguished by IR spectroscopy. Generally, intermolecular H-bonding gives rise to broad bands whereas intermolecular H-bonds give rise to sharp and well defined bands.

Applications of IR Spectroscopy
i) Determination of Molecular Structure:

IR spectroscopy is very useful in determining the molecular structure of unknown compound. The absorption bands in the functional group region tell about the functional groups present in the molecule while those in the fingerprint region give information about the structure of the molecule, particularly about the patterns of substitution. Thus, a careful analysis of the IR spectrum may lead to the molecular structure of the compound under study.

ii) Identity of the Compounds: IR spectroscopy is used to establish the identity of a given compound. Due to appearance of a large number of absorption bands in the IR spectra of organic compounds, the probability that any two compounds will produce identical spectra is practically zero. Thus, if two samples afford identical spectra under similar conditions of measurement, they must be the samples of the same substance.

IR spectra of two enantiomeric compounds taken under similar conditions are exactly the same and hence, they cannot be distinguished by IR spectroscopy.

iii) Testing the purity of sample: It is possible to test the purity of a given sample by comparing its IR spectrum with that of a pure sample. The spectrum of pure sample is sharp and well defined and while that of crude and impure is blurred, has broad and poorly resolved

absorption bands. For example, the impurity of a ketone in an alcohol leads to a relatively poor spectrum having additional absorption bands due to the carbonyl group.

iv) It is useful to study the progress of chromatographic separations.

v) It has been useful to study inter-molecular and intramolecular H-bonding.

vi) Quantitative analysis: The quantitative determination is based on the determination of concentration of one of the functional groups of compounds being estimated. Suppose there is a mixture of hexane and hexanol and then concentration of hexanol can be determined by measuring absorption of OH bonds. The formula used will be: A = - log ( I / Io ) = abc where, A = absorbents I = intensity of radiations after leaving the sample Io = intensity of radiation before entering the sample a = absorbtivity of cell b = initial path length of sample cell

c = concentration of the solution If a and b are constant, AC Hence, C can be measured by knowing A.