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IR SPECTROSCOPY
Manu Jose First year M.Pharm Pharmaceutical Analysis Dept. National College of Pharmacy

OVERVIEW
INTRODUCTION THEORY FACTORS AFFECTING VIBRATIONAL FREQUENCY

SAMPLING TECHNIQUES
INSTRUMENTATION

INTERPRETATION
APPLICATION

Introduction

Spectroscopy
Spectroscopy is the measurement and interpretation of EMR absorbed or emitted,

when the organic molecule or atoms or ions of a

sample move from one energy state to another.

Definition
IR spectroscopy can be defined as a method for the identification of substances based on their

absorption of IR wavelength.

IR RADIATION

Electromagnetic spectrum

g-rays

X-rays

UV

IR

Microwave

Radio

Visible

Wave number Near IR Mid IR Far IR 14000-4000cm-1 4000-400cm-1 400-10cm-1

Wave length 0.8-2.5m 2.5-25m 25-1000m

Theory
IR radiation in the range 10,000- 100 cm-1 is absorbed. Frequency of absorption depends on relative masses, the force constant, and geometry of atoms. Converted to energy of molecular vibration. The absorption is quantized. Vibrational spectra is appear as bands.

A molecule absorbs a selected frequencies of IR.

Absorption corresponding to 8-40 KJ/mol

Not have sufficient energy to cause the excitation

of electrons, it can cause vibrations.

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Criteria for absorption

Not all bonds are capable of absorbing IR. 1. Dipole moment To absorb IR, a molecule must undergo net change in dipole moment as it vibrate. Electric field of radiation can interact with molecule- change amplitude of vibration. Eg: Hydrochloride.

2. Correct wavelength
Applied IR frequency =Natural frequency of vibration

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Calculation of stretching frequency:

By Hooks law;

v - vibrational frequency k - force constant = (m1.m2)/(m1+m2) m1 and m2 mass of atom 1 and 2 respectively.

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Molecular vibrations

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The relative positions of atoms in a molecule are not fixed but fluctuate continuously as a

consequence of vibrations and rotations.

Two types of fundamental vibrations are there,

Stretching
Bending

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Stretching vibrations
Involves continuous change in inter atomic distance along the axis.
Two types:
Symmetrical stretching-stretching/ compression in symmetrical way.

Asymmetric stretching-one bond is stretching while other is compressing.

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symmetrical
H

C
H

asymmetrical
H

C
H

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Bending vibrations:
Involves change in bond angle between bonds with a common atom or the movement of group of atoms to the reminder of molecule.

Two types:
In-plane
Out-of plane

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In plane bending vibrations Scissoring- atoms move towards and away from each other.
H C H

Rocking- The structural unit swings back and forth in the plane.

H C H

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Out of plane bending vibrations

Wagging: The structural unit swings back and forth out of the plane
Twisting: structural unit rotate about the bond which joins to the rest of the molecule

H C H

H C

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Degree of freedom
Each atom has 3 degrees of freedom N-atom molecule there will be 3N degree of freedom. Translation - the movement of the entire molecule while the positions of the atoms relative to each other remain

fixed
Rotational transitions inter-atomic distances remain constant but the entire molecule rotates with respect to three mutually perpendicular axes.
Translation Non linear linear 3 3 Rotational 3 2

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Number of vibrational degree of freedom

For molecules having N atoms in them Nonlinear molecules= 3N - 6 Eg : H2O (3x3)-6=3

Linear molecules= 3N -5
Eg : N2 (3x2)-5=1

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Why not 3N-6/3N-5 bands in IR Spectrum?

The theoretical number of fundamental vibrations (absorption frequencies) will seldom be observed. Overtone and combined tone increase the number of bands.

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Reasons for decrease in number of bands are-

Bands which are so close that they coalesce.

Bands which are too weak to be observed.

Occurrence of a degenerate band.

Lack of change in molecular dipole moment.

Fundamental frequencies outside 4000-400 cm-1

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Eg:

CO2 is linear 3x3-5 =4 degree of freedom. But

Symmetric stretching- no change in dipole Bending vibrations are equivalent (degenerate)

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Factors influencing vibrational frequencies

Calculated value of frequency of absorption for a
particular bond is never exactly equal to its experimental value.
Electronic effects inductive and field effect Ring size Hydrogen bonding Vibrational coupling

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Inductive effect:
Electro negative/ Stronger bond Negative inductive Increased force constant Wave number rises Acetone chloroacetone Dichloroacetone Tetrachloroacetone H-CHO Electro positive/ electron attracting Positive inductive effect Weaker bond Decrease force constant Wave number decreases CH3-CHO 1745 Wave no cm-1 1715 1725 1740 1778 1750

electron withdrawing

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Field effect:
Lone pair of electrons on two atoms influences

each other through space, can change vibrational

frequency of both groups.

Eg: O- haloacetophenone
CH3 C = O: :

Electrostatic repulsion due to lone pair off electrons

Change the state of hybridization of C=O

X:
:

Absorption occurs at higher wave number

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Ring size
Ring strain causes large shift to higher frequency
7 membered ring 1702 cm-1 6 membered ring 1715 cm-1 5 membered ring 1745 cm-1 4 membered ring 1780 cm-1 3 membered ring 1850 cm-1

Increased s character

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Hydrogen bonding
Remarkable downward frequency shift. Stronger H bond- greater the shift towards lower wave number.
Free alcohol H bonded alcohol - sharp OHstr band - broad OHstr band

OH of phenol condensed to polymeric wide

envelope of O-Hstr

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Vibrational coupling
Isolated C-H bond only one str frequency

For methylene (-CH2-) two coupled vibrations of

different frequency. ( asymmetric and symmetric)

Fundamental+ fundamental

Amide

1600- 1700cm-1

C=O str N-H def

Fundamental + overtone

Aldehydes

2800- 2700 cm-1

C-H str C-H def

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Sampling techniques

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1) Solid samples:
Mull technique Pressed pellet technique Solids run in solutions Solid film

2) Liquid samples 3) Gaseous sample

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Mull technique: Grinding 2-5mg of sample in smooth agitate mortar. Powdered sample + Nujol paste Paste between the two plates of salt. The oil has few absorption bands at 2857, 1449 and 1389 cm-1

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Pressed pellet technique:

1mg Sample+ 100mg KBr powder
pressed in hydraulic press transparent disc inserted in sample holder.

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Solids films: Amorphous solid samples melted between salt plates allowed to form solid film. For qualitative purpose.

Solids run in solution Solid + suitable solvent solution Kept in cells for liquids Solvents- non associated solvents- CS2, CCl4,

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Liquid sample:

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Gaseous sample:
Vapors in specially designed cells.

End walls made up of

Sodium chloride.

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Instrumentation

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Dispersive infra red spectrometers

Instrument produce a beam of IR radiation Mirrors divide it into 2 parallel beam of equal intensity. Sample is placed in one beam, other is used for reference. The beam is then passed through monochromator which disperse into a continuous spectrum. The detector senses the ratio b/w intensities of sample and reference beam. Signals is amplified and recorded.

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Dispersive infra red spectrometers

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Radiation sources
Consist of inert solid Heated electrically
Nernst glower Globar source Mercury arc Incandescent wire source Tungsten filament

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Nernst glower
Composed of rare earth oxides- zirconium, yttrium and thorium Hollow tube (2-5cm x 1-3mm) Platinum leads at one end Large negative temp. coefficient. Emit radiation over wide range and remains steady over a long period.

Disadvantages: Fragile Auxiliary heater Over heating

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Globar source
Rod of sintered silicon carbide. (5cm x 5mm). Positive coefficient of resistance. Self starting and electrically heated Enclosed in water cooled brass tube

Less intense.

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Mercury arc
For far IR region High pressure Hg arc, enclosed in quartz jacketed tube, at 1 atm Passage of electricity through vapor internal

plasma source IR radiation

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Incandescent wire loop

Tightly wound spiral of Nichrome wire. No water cooling Less maintenance Less intense than other sources.

Tungsten filament lamp

Tightly wound spiral of tungsten wire. For near IR

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Sample holders
Constructed of rock salt. Path length is adjusted with Teflon. Filled and emptied with hypodermic needles.

Foggy due to moisture.

Care:
Moisture free samples Fingers should not be come in contact Prevent contamination with silicones

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Monochromator
To select desired frequency from radiation source.
Prism monochromator Grating monochromator

Material used: Halogen salt

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Detectors
Thermal detectors
(IR heating potential difference amt of radiation)

Thermocouple Bolometer Golay cell

Photo detectors

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Thermocouple

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Bolometer

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Golay cell

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FT Optical System Diagram

Light source

He-Ne gas laser

(ceramic) Beam splitter Movable mirror Sample chamber

(DLATGS) Fixed mirror Interferometer Detector

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Michelson interferometer FT-IR

Moving mirror

IR Source Stationary mirror

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Constructive and destructive interferences

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Comparison

Dispersion Spectrometer
The dispersion Spectrometer takes several minutes to measure an IR spectrum Also the detector receives only a few % of the energy of original light source.

FT-IR
FT-IR takes only a few seconds, to measure an IR spectrum. The detector receives up to 50% of the energy of original light source.

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Spectrum

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IR spectrum

Each dip- band 100% transmittance- no absorption. Scale of spectrum is not entirely linear.

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Interaction of IR Radiation with Organic Molecules

Primary use is to detect functional group. All organic functional groups are made up of multiple bonds and therefore they will show multiple IR bands. Capable of giving sufficient information about the structure of a compound.

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ALKANES
General structure :
R- CH2- R

Wave number
C-H (str) 3000-2840 cm-1

C-H (def)

1470-1450 cm-1

C-H (rock)

1370-1350 cm-1

In long chain alkanes

C-H (rock)

725-720 cm-1

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Eg: Octane

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ALKENES
General structure : R-C=C-R
Wave number

=C-H str =C-H def C=C str

3100-3000 cm-1 1000-650 cm-1 1680-1640 cm-1

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Eg: 1-Octene

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ALKYNES
General structure : R- C C - R
Wave number - C C - H str 3333-3267 cm-1

- C C - H def

700-610 cm-1

-C C str

2260-2100 cm-1

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Eg: 1-Hexyne

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Aromatic Compounds
General structure : Ar-R Wave number

C -H str

3100-3000cm-1

C -C str (in ring)

1600-1585cm-1 1500-1400cm-1

C-H bend

900-675cm-1

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Eg: Toluene

Alkyl Halides
General structure : R-X
Wave number
C-H str 3000-2850 cm-1

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C-H def

1300-1150 cm-1

C-X str eg: C-Cl str C-Br str

850-515 cm-1 850-550 cm-1 690-515 cm-1

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Eg: 1-Bromopropane

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Alcohols
General structure : R-OH
Wave number

O-H str

3500-3200 cm-1

C-O str

1260-1050 cm-1

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Eg: Ethanol

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KETONES
General structure : R-CO-R
Wave number
C=O str

aliphatic ketones

1715 cm-1

,-unsaturated ketones

1685-1666 cm-1

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Eg: 2-Butanone

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Aldehydes
General structure : R-CHO
Wave number

H-C=Ostr
C=O str

2830-2695 cm-1

aliphatic aldehyde

1740-1720 cm-1

,-unsaturated aldehydes

1710-1685 cm-1

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Eg: Butaraldehyde

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CARBOXYLIC ACIDS
General structure : R-COOH
Wave number O-H str 3300-2500 cm-1

C=O str

1760-1690 cm-1

C-O str

1320-1210 cm-1

O-H bend

1440-1395 cm-1 950-910 cm-1

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Eg: Hexanoic acid

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ESTERS
General structure : R-COOR

Wave number
C=O str

aliphatic esters

1750-1735cm-1

,-unsaturated

1730-1715cm-1

C-O str

1300-1100cm-1

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Eg: Ethyl acetate

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Amines
General structure : R- NH2 Wave number N-H str 1O amines 3400-3250cm-1 3400-3300cm-1 3330-3250cm-1 3350-3310cm-1

2Oamines

3O amines
N-H bend (1O only) N-H wag C-N str aromatic amines aliphatic amines

no bands
1650-1580cm-1 910-665cm-1 1335-1250cm-1 1250-1020cm-1

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Eg: Aniline

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NITRO GROUP
General structure: R-NO2
Wave number

N-O str (asymmetric)

1550-1475cm-1

N-O str(symmetric)

1360-1290cm-1

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Eg: Nitromethane

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Recent Advancements

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Attenuated Total Reectance Spectroscopy ( ATR Spectroscopy)

Utilizes the phenomenon of Total Internal Reection Angle of incidents > critical angle The beam penetrates a fraction of a wavelength beyond the reecting surface.

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when a material that selectively absorbs radiation, the beam

loses energy at the wavelength

where the material absorbs. The resultant attenuated radiation is measured. plotted as a function of wavelength and gives rise to the absorption spectral characteristics of the sample.

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Applications

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Quantitative analysis
Based on the determination of the concentration of one of the functional group of the compound being estimated. Concentration is determined using Beer- lamberts law A = I1/I0 = abc A c ;

a and b are constant.

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Qualitative analysis
By comparison with reference spectra. Group frequency region: (3700-1500cm-1)
Hydrogen bonding region
By str vibration between hydrogen and other atom (O-H)

Triple bond region

Triple bond produce a peak in the region 2700-1850 cm-1

Double bond region

Compound having double bond- peak at 1850- 1500cm-1

Finger print region: (1500-700cm-1)

Identity of a compound Due to bending vibrations

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Miscellaneous applications
Study of progress of reaction. Detection of impurities. Tautomerism. Functional group identification.

Presence of water in sample.

Industrial applications.

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Conclusion
Infrared spectroscopy is certainly one of the most important analytical techniques available to todays scientists for the determination of identity and molecular structure of organic compounds

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References

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William Kemp; Organic Spectroscopy; 3rd edition; page no:20-94. Robert M Silverstein; Spectrometric Identification of Organic Compounds; 6th edition; page no:71-109. Skoog, Holler, Crouch; Instrumental Analysis; 5th edition; page no:477- 528. John R Dyer; Application of Absorption Spectroscopy; page no:23-33.

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H.Kaur; Instrumental Method of Chemical Analysis; 6th edition; page no:181-184,192-195. P.S Kalsi Spectroscopy of organic compound; 6th

edition, page no 67,74.

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