SPECTROSCOPY

P. Nagaraja
Assistant Professor in Chemistry
IIIT, RK Valley, RGUKT-AP

Contents: Introduction to Spectroscopy

Infrared spectroscopy – Principle, Modes of vibrations, Signal
characteristics-Wave number, IR spectrum, Identifcation of functional groups
using IR
UV spectroscopy – Principle, Beer-Lambert’s law, electronic transitions,
Chromophore and auxochromes, Conjugation and color
 Introduction
• The study of interaction between matter and electromagnetic
radiation (EMR) is called spectroscopy
• Types : Based on type of matter, they may be
• EMR + Atoms Atomic spectroscopy
• EMR + Molecules Molecular spectroscopy
• Based on study
• Absorption spectroscopy: If absorbance of light is
recorded as a function of wavelength, it is known as
absorption spectroscopy
• Emission spectroscopy: If emission of light is recorded as a
function of wavelength, it is known as emission spectroscopy
 Electromagnetic radiation
• Electromagnetic radiation (EMR): EMR is a form of energy consists of
oscillating electric and magnetic feld which are perpendicular to each
other.
• EMR is characterized by its wavelength and frequency

Wavelength: The distance between two Frequency: The number of cycles

crests or troughs is called wavelength passing through a point in 1 second
Wavelength is represented as Lambda (λ) Frequency is represented as Nu (υ)
Units : nm or cm or m Units : Cycles/sec or Hertz
 Electromagnetic radiation

Source: Organic Chemistry, 3rd edition, Janice Gorzynski Smith

 Electromagnetic spectrum
The arrangement of EMR in the decreasing order of their energies is known as electromagnetic spectrum

Shorter Longer
wavelength wavelength
High frequency Low frequency
high energy Low energy

Source: Organic Chemistry, 3rd edition, Janice Gorzynski Smith

Condition for absorption of EMR

Source: Organic Chemistry, 3rd edition, Janice Gorzynski

Smith
 Energy levels in matter &
Types of molecular spectroscopy
UV-Visible spectroscopy or Electronic
spectroscopy
It involves the interaction between matter and UV-
Visible radiation and the molecule undergo
electronic excitation

IR spectroscopy or Vibrational spectroscopy

It involves the interaction between matter and
infrared radiation and the molecule undergo
vibrational excitation

Microwave spectroscopy or Rotational

spectroscopy
It involves the interaction between matter and
microwave radiation and the molecule undergo
Fig. Diferent energy levels in a molecule rotational excitation

NMR spectroscopy
It involves the interaction between matter and
 Infrared(IR) Spectroscopy
• It involves the interaction between matter and infrared
radiation
• The energy associated with IR is smaller hence it causes
excitation only between vibrational energy levels
• IR energy ranges between 4000-400 cm-1
• IR spectrum is a graph between *wavenumber (cm-1) on
x-axis and % transmittance on y-axis
• IR spectroscopy gives information about the nature of
functional group present in the given organic compound
*Wave number is the number of waves in 1 cm. Energy α υ. Units: Cm-1
 Modes of vibrations
• Covalent bonds are more like springs with weight at each end
• When two or more atoms are bonded to each other, the bonds undergo
stretching and bending with certain vibrational frequency

• The vibrations are quantized so they occur at specifc frequencies

• The vibrational frequency of covalent bonds corresponds to IR light
• When frequency of IR light matches with frequency of vibration, IR light
will be absorbed and gives a signal
• Diferent kinds of bonds vibrate at diferent frequencies, so they absorbs
diferent frequencies of IR light
Source: Organic Chemistry, 3rd edition, Janice Gorzynski
 Stretching and bending vibrations

A stretch is a vibration occurring along the line of the bond

A stretching vibration changes the bond length
Stretching vibration may be symmetric or asymmetric

A bend is a vibration that does not occur along the of

the bond
A bending vibration changes the bond angle
Bending vibration may symmetric and asymmetric
and they may be in plane and out of plane

Source: Organic Chemistry, 8th edition, Paula Yurkanis Bruice

 The intensities of IR bands
• A vibration that accompanied by change in dipole moment
is said to be IR active
• O=C=O O==C==O (no change in dipole, IR inactive)
• O=C=O O===C=O&O=C===O (change in dipole, IR active)
• When a bond stretches, there is a increase in its dipole
moment
• The intensity of IR band depends on the size of the dipole
moment change
• Intensity of IR band α size of the dipole moment
•
 IR spectrum

• IR spectrum can divided into two regions

• 1. Functional group region
• It ranges 4000-1500 cm-1 in IR spectrum
• It involves mostly stretching mode of vibrations
• It gives information about nature of functional group in molecule
• 2. Finger print region
• It ranges 1500-400 cm-1 in IR spectrum
• It involves mostly bending mode of vibrations
• This region is complex and unique for a given compound
Source: Organic Chemistry, 3rd edition, Janice Gorzynski
 Vibrational frequencies of bonds and Hooke’s law

The frequency of region at which a bond can

vibrate can be found from Hooke’s law

Source: Organic Chemistry, 3rd edition, Janice Gorzynski

 IR frequencies of Hydrocarbons
Alkanes Alkenes Alkynes
sp3 C-H, 3000-2850 cm-1 sp2 C-H, 3100 cm-1 sp C-H, 3300 cm-1
C-C, <1500 cm-1 C=C, 1650 cm-1 C C, 2250 cm-1

Source: Organic Chemistry, 3rd edition, Janice Gorzynski

Smith
 IR frequencies of Oxygen containing
compounds
Alcohols Ethers Carbonyl compounds
sp3 C-H, 3000-2850 cm-1 sp3 C-H, 3000-2850 cm-1 sp3 C-H, 3000-2850 cm-1
O-H, 3600-3200 cm-1 -- *C=O, 1750-1700
*The vibrational frequency of C=O depends on type of carbonyl compoun
C-O, 1050 cm-1 C-O, 1050 cm-1 --

υ↓
υ↑

Type of ~ C=O frequency

Carbonyl (cm-1)
Ketone 1715
Aldehyde 1730
Carboxylic acid 1720
Ester 1740
Amide 1690
Source: Organic Chemistry, 3rd edition, Janice Gorzynski
 IR frequencies of Nitrogen containing
compounds
Amines Amides Cyanides
sp3 C-H, 3000-2850 cm-1 sp3 C-H, 3000-2850 cm-1 sp3 C-H, 3000-2850 cm-1
N-H, 3400-3300 cm-1 *N-H, 3400-3200 cm-1 -CN, 2250 cm-1
C-N, <1500 cm-1 C=O,
o 1690 cm
-1
--o
*For amides, in N-H region 1 amines gives 2 peaks, 2 amines
gives 1 peak
3o amines gives no peak (only C=O peak)

Reference: Organic Chemistry, 3rd edition, Janice

Gorzynski Smith
 Strategic problems-1

Reference: Organic Chemistry, 3rd edition, Janice Gorzynski Smith

 Data based problems

Source: Organic Chemistry, 3rd edition, Janice Gorzynski Smith

 Strategic problems-2

Source: Organic Chemistry, 8th edition, Paula Yurkanis Bruice

 UV-Visible spectroscopy
• It involves the interaction between matter and UV-visible radiation
• The energy associated with UV is higher hence it causes excitation
between electronic energy levels
• UV energy ranges between 200-400 nm and visible region ranges
400-800 nm
• UV spectrum is a graph between wavelength (nm) on x-axis and %
absorbance on y-axis
• UV-Visible light causes π to π* transitions and hence only
compounds with π bonds gives UV/vis spectra
• IR spectroscopy gives information about the conjugation and
concentration of the given organic compound.

Reference: Organic Chemistry, 8th edition, Paula Yurkanis Bruice

 Types of Electronic transitions

Transitions observed in UV/Vis region are

Possible electronic transitions
π → π * (Strong & Higher energy transition)
1) σ → σ* (In alkanes)
n → π * (Weak & Lower energy transition)
2) π → π * (In alkenes, aromatics)
3) n → σ* (In alkylhalides, alcohols)
4) n → π * (In carbonyl compounds)
The decreasing energy order of electronic transitions is, σ → σ* > n → σ* > π → π * > n → π *
 Beer-Lambert’s law
• It was proposed by Beer and Lambert independently and it gives
information about the concentration of sample at a given wavelength
• It states that, the amount of light absorbed by the sample is directly
proportional to its concentration and length of the light path

• Mathematically, A = c.l.ε
• A = absorbance, c = concentration of the sample (mol/L)
• l = length of light path(cm), ε = Molar absorptivity (M-1.cm-1)

• The molar absorptivity is a constant that is characteristic of the compound at a

particular wavelength
• ε is defined as the absorbance of compound when c = 1.00 M and l = 1.00 cm

Reference: Organic Chemistry, 8th edition, Paula Yurkanis Bruice

 Sample problems

Application of Beer-Lambert’s law

 Beer-Lambert’s law is used to fnd the concentration of

unknown sample through calibration method
 In this method, several standard solutions are prepared
and their absorbance are measured at specifc λ
 A calibration graph is made from the above data
 Now the absorbance of unknown sample is measured and
its concentration can be found by intersecting a line on x-
axis
 Chromophore and Auxochrome
Chromophore: Chromophore is the part of a molecule that absorbs UV or
visible light
Examples: -C=C-, -C=O, -N=N- etc. groups in a molecule can act as
chromophore

Auxochrome: Auxochrome is a substituent, when attached to a chromophore,

alters both the λmax and intensity of the absorption
Examples: -OH, -NH2 etc. groups in a molecule can act as chromophore

An auxochrome do not absorb UV/vis light but alters the λmax by extending the
conjugation

λmax refers to the wavelength where a substance has its strongest

photon absorption
Source: Organic Chemistry, 8th edition, Paula Yurkanis Bruice
 Effect of conjugation on λmax
• λmax refers to the wavelength where a substance has its strongest photon
absorption
• The UV/vis light induces electron transition from ground state to excited state
of the molecule
• Ground state is called highest occupied molecular orbital (HOMO) while
excited state is called lowest unoccupied orbital (LUMO)
• The wavelength of absorption in UV depends on energy gap between HOMO
and LUMO
• The energy gap between HOMO and LUMO decreases as the extent of
conjugation increases LUMO

HOMO
Why λmax increases with conjugation

Lower energy = Longer wavelength

 The Visible spectrum and color

If the conjugation is more extended, the wavelength of absorption falls to visible region and the
compound gets colored
Example : Carotene in carrots, Lycopene in tomato & watermelon
The relationship between the wavelength of the light absorbed and observed color can be
known from color wheel
 When a molecule absorbs light, all non-absorbed light combines to produce the complement
of the absorbed color
 If red is absorbed it appears as green. If it absorbs violet it appears yellow
 When two diferent colors of light is absorbed, then it appears as the combination of two
refected colors.
 For example, if Reference:
red and violet colors
Organic are absorbed
Chemistry, it appears
8th edition, to beBruice
Paula Yurkanis yellow green