Applied Chemistry

Unit-4

SPECTROSCOPY

Department of Applied Chemistry

Bhilai Institute of Technology, Durg (C.G.)
B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-4
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 SYLLABUS
UNIT – IV: Spectroscopy CO4
Introduction: Electromagnetic Radiation, Lambert Beer‟s Law, Ultra Violet Spectroscopy:
electronic transitions, selection rules, auxochrome, chromophore, Instrumentation,
Applications: Quantitative & qualitative analysis, Simple numerical based on absorption
laws. Infrared Spectroscopy- Introduction, Principle: diatomic & poly atomic vibrations,
selection rule, functional & Fingerprint Region, Instrumentation. Qualitative applications.
[8Hrs]

Course Outcome:
CO4: Discuss the principles, instrumentations and applications of UV & IR techniques.

UNIT-4
SPECTROSCOPY
1. Introduction: The transitions of the electrons from one energy level to another
energy level of the atom results in emission or absorption of electromagnetic
radiations and the energy difference between the involved energy levels gives spectral
lines in different regions, thereby giving rise to atomic spectra, which provide useful
information, about the atomic structure. Similarly, molecular spectra (emission or
absorption) provide useful informations regarding the molecular structure. Molecular
spectroscopy may be defined as “the study of interaction of electromagnetic radiations
with molecules”.

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Fig. 1. The electromagnetic spectrum specifying different spectral regions. The bands at
the bottom indicate the type of transitions that absorbs (or emit) in the various regions.

2. Types of energy present in molecules:

1. Translation energy (Etrans) is concerned with the overall movement of the molecules
along the three axes. It is significant only in gases and to lesser extent for liquids.

2. Rotational energy (Erot) involves the spinning of molecules about the axes passing
through their center of gravity.

3. Vibrational energy (Evib) is associated with vibrations within a molecule such as the
stretching or the bending of bonds.

4. Electronic energy (Eelec) involves changes in the distribution of electrons by the

promotion of electrons to higher levels on absorption on energy. Now, if E is the energy of a
molecule, it can be expressed as:

E=E tans +E rot +E vib +E elec

Fig. 2 (a) shows rotation about two axes while (b), (c) and (d)
show vibration within the molecule.

Types of spectra:

(i) Emission spectra: Molecules give emission spectra when subjected to intense heat or
electric discharge. The molecules obtain the necessary energy to become excited. On
returning to their lower energy state, molecules may emit radiation, which is the result of a
transition of a molecule from an excited state to one of lower energy, usually the ground
state. This excess energy is emitted as a photon and the corresponding frequency is recorded
as the emission spectrum. If the transition is from upper energy level (E2) to lower energy
level (E1), the frequency (v) of the emission spectrum is given by:

E2  E1  E
v 
h h

(ii) Absorption spectra: When a substance is irradiated with electromagnetic radiation, the
energy of the incident photons may be transferred to the molecules, raising them from the
ground state to an excited state. This process, is known as absorption and the resultant
spectrum, is known as absorption spectrum. Energy absorption occurs only when the energy
difference between the ground state and higher energy level is exactly matched by the energy
of the incident electromagnetic radiation. The energy absorbed ( E ) by a molecule may

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bring about changes in one or more of its energy levels such as rotational, vibrational and
electronic.

3. General Features of Absorption Spectrometer: The instrument used to record the

spectra of molecules, is called a spectrometer. The exact design of the instrument varies
according to the spectral region being examined, but the basic features of all spectrometers
are similar. A generalised schematic representation of spectrometer is shown in Figure.

Fig. 5: Layout of spectrometer (schematic)

The absorption spectrometer consists of:

(a) A suitable source of electromagnetic radiation;

(b) A system to analyse the radiation or a monochromator and

(c) An appropriate detector to detect the intensity of the radiation absorbed.

The final absorption spectrum is displayed either on a video screen or, more generally,
recorded on a chart paper. In this manner, we can measure the extent to which a substance
absorbs radiation at each wavelength (or frequency or wave number).

4. Ultraviolet (UV) and Visible (VIS) Spectra: Absorption of radiation in the ultraviolet
(wavelength range 200 - 400 nm) and visible (wavelength range of 400 – 750 nm) regions of
the electromagnetic spectrum results in transitions between electronic level, because the
energy changes are relatively large and this corresponds to 100 - 100,000 kJ mol–1. Every
molecule can undergo electronic transitions. The large energy changes involved in electronic
transitions also cause simultaneous change in vibrational and rotational energies. This is
because Eelec  Evib  Erot . Due to the reason, the UV and VIS spectra of even simple
molecules in the gaseous state exhibit narrow absorption peaks, and each peak represents a
transition from a particular combination of vibrational and rotational levels in the electronic
ground state to an another different combination of vibrational and rotational levels in the
excited state.

Origin of absorption bands in UV and visible spectra: According to molecular orbital

theory, the interaction of atomic orbitals leads to the formation of “bonding” and
“antibonding” molecular orbitals. Depending upon the nature of the atomic orbitals involved,
the bonding orbitals may be of:

(i) Sigma ( ) type, in which the electron density is concentrated along the internuclear axis,
or

B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-4

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(ii) Pi ( ) type, in which the electron density is concentrated above and below the
internuclear axis.

Fig. depicts the electron density probability contours for electrons occupying (a)  and 
(bonding) and (b)   and   (antibonding) orbitals while Fig. 24 (b) depicts the relative
energies of bonding, antibonding and nonbonding (n) molecular orbitals.

Fig. : Shapes and relative energies of molecular orbitals: (a) bonding and antibonding
orbitals, (b) relative energies of orbitals and possible transitions between them.

When excitation occurs, an electron from one of the filled  ,  or n molecular orbitals get
excited to vacant   or   (antibonding) molecular orbitals. Corresponding to possible
excitations, there are various absorptions:

   ;    ; n   ;

   ;    ; n   

Since  electrons require a high energy for excitation to  , so order of decreasing energy
for the absorption is:

                    n     n   
Transition accounting for absorption in the 200-800 nm region of electromagnetic radiation.

Out of the above possible transitions, the last three ones account for the absorption in 200 -
800 nm region of electromagnetic radiation. On the other hand, first three transitions require
much higher energy, so only molecules with n or  electrons give rise to characteristic
spectra in the region 200 - 800 nm of electromagnetic radiation. It may be pointed that
alkanes absorb in region below 200 nm.

It may be added here that the part of the molecule having n or  electrons is essentially
responsible for absorption, and these fragments, are known as chromophones.

Simple chromophones:

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 C= C,  C  C,  C  N,  N = N, C= O

undergo     transitions in short wavelength regions of ultraviolet radiations.

Polar groups such as  OH, OR,  NH 2 ,  SH and  X (halogen) having unshared pair of
electrons and may show absorption above 190 nm. Such groupings, are called auxochromes,
when conjugated with chromophones, since they modify the position of absorption band
relative to that of the parent chromophore alone.

Instrumentation: In visible-UV spectrometer, a beam of light is split into two equal halves.
One-half of the beam (the sample beam) is directed through a transparent cell containing a
solution of the compound being analyzed and one-half (the reference beam) is directed
through an identical cell that contains only the solvent. The instrument is so-designed that it
can compare the intensities of the two beams at each wavelength of the region.

Fig. Schematic diagram for a typical visible-UV spectrometer.

If the compound absorbs light at a particular wavelength, then intensity of the sample beam
(I) will be less than of the reference beam ( I 0 ). The instrument gives output graph – a plot of
the wavelength of the entire region versus the absorbance (A) of the light at each wavelength,
I 
where absorbance ( A)  log  0  . Such a graph is known as an absorption spectrum.
 I 

Absorption Laws:

Lambert Law: Suppose a monochromatic radiation is passed through a transparent medium

and IO is the intensity of incident radiation and I is the intensity of radiation at a thickness of
l, then the rate of change of intensity with respect to thickness will be proportional to I.

dI
 I
dl

dI
  k dl
I

where k  proportionally constant on integration.

dI
  k  dl
I

 log e I  kl  C

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when l  0, I  I O

 log e I O  0  C

log e I  kl  log e I O

I
log e   kl
IO

Limitations: For most of the time it is not convenient to observe absorbed radiation in solid
transparent medium and we need to prepare transparent solution of the substance under
examination.

Beer’s Law: Beer‟s law is given for transparent solution of the substance. According to this
law “The fraction of the monochromatic radiation absorbed on passing through a transparent
solution of a substance is directly proportional to the concentration of the absorbed medium”.

dI
  .C.l
I

C  Molar concentration of solution

 Molar absorption coefficient

l  Path length
x
I  IO e .C .l

I
or log e   x .c.l
IO

I 
log  . c. l
IO 2.303

IO
log  . c. l
I

2
where 
2.303

 known as molar extinction coefficient

IO
The quantity log  . c. l is termed as absorbance „A‟.
I

IO
 A  log  . c. l
I

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Numericals:

Q. 1. Calculate the molar absorptivity of a compound with Mol. wt. 144 of its 10–5 g / ml
solution exhibits an absorbance of 0.4 when the path length is 1 cm.

105 103
Solution: Molar concentration C  mol./lit
144

Path length l  1 cm

Absorbance A = 0.4

A 0.4  144
 
c. l 10 2  1

= 5760

Q. 2. Calculate absorbance of 3.4 104 M coloured solution of an iron complex which has
molar absorptivity of 320 at 580 nm? (The path length being 1 cm.)

Solution: A = E.C.l.

 320, C  3.4 104 m, l  1 cm

A  320  3.4 104 1

 1088 104

= 0.108

I
Transmittance: The ratio is known as transmittance.
IO

IO
A  log
I

I
A   log   log T
IO

I
The % transmittance   100
IO

Applications of UV spectroscopy: In predicting the relation between different groups,

especially w.r.t. conjugation existing between:

(i) two or more C – C multiple bonds (double or triple);

(ii) C – C and C – O double bonds, or;

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(iii) C – C double bonds and aromatic benzene ring. Thus, UV spectroscopy have been of
great help in determining the structure of several vitamins, detecting steric hindrance, study
rates of reactions, determination of dissociation constants of acids and bases from the change
of absorption spectra with pH. However, UV spectroscopy is not helpful in the detection of
individual functional groups.

5. Infrared (IR) Spectra: Electromagnetic radiation in the infrared region of the spectrum
(3 1012 or 3 1014 Hz or 100 cm 1 to 104 cm 1 ) results in changes of the vibrational energy
of molecules. The energy change required for molecular vibrations is of the order of 1 to 100
kJ mol–1. The changes in vibrational energy levels are accompanied by transitions between
rotational levels also. Consequently, each line in vibrational structure is accompanied by the
rotational fine structures. Evidently, such a spectrum, is known as vibrational-rotational
spectrum. However, if the rotational fine structure is not considered, then absorption, is
known as vibrational spectrum.

Requisite for IR spectra: All type of molecules cannot interact with IR radiation. Only those
molecules which exhibit change in dipole moment during a vibration can exhibit infrared (IR)
spectra. Evidently, homonuclear diatomic molecules (e.g., H2, O2, N2 or Cl2) do not show
change in dipole moment during vibration. Consequently, these do not exhibit infrared
spectra.

The quantum theory predicts that permitted vibrational energies (Evib) are governed by the
expression:

1
Evib  v  h v0
2

Where v is the vibrational quantum number, with possible values of 0, 1, 2, etc. and v0 is the
fundamental frequency.

1 3
The lowest two energy levels, v = 0 and v = 1, possess Evib values of hv0 and hv0 ,
2 2
respectctiely, and the difference between them (i.e., the energy of the v  0  v  1
transition) is hv0 . The appropriate frequency of the electromagnetic radiation associated with
this energy change, is the fundamental frequency (v0 ). It may be noted that even in the
1
ground vibrational state, the molecules has the vibrational energy  hv0 . This is called the
2
zero point energy, which signifies that a molecule must always vibrate and can never be at
rest. It may be pointed that the vibrational energy levels are much more widely spaced than
the rotational energy levels.

When a molecule absorbs energy in the infrared region of electromagnetic spectrum, it can
change its vibrational and rotational levels and these energy changes account for the features
of IR spectrum. However, such a spectrum is much complicated, due to the rotational fine
structure [see Fig. 6(a)]. But this complication can be avoided by taking IR spectrum for
liquid or in solution or solid sample. Under such conditions, the rotational fine structure

B.Tech. First / Second Semester, BIT Durg, Applied Chemistry; Unit-4

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becomes buried and consequently, a broad peak is observed for a vibrational change only.
Consequently, the interpretation of the IR spectra is made simple even for polyatomic
molecules.

Selection rule for a harmonic vibrational transition: From the solution of Schrodinger
equation, we get  v  1, i.e., the increase or decrease in the vibrational quantum number is
by one unit only. In other words, the energy difference between two vibrational levels
involved in a transition would always be equal to spacing ( hv0 ). consequently, all lines in the
spectrum fall in the same place. (see fig.)

Fig. : The allowed vibrational energy levels and the transitions between them.

Applications for IR spectroscopy: (1) In establishing the identity of the compounds: The IR
spectrum of the compound is compared with that of known compounds and from the
resemblance of the two spectra, the nature of the compound can be established.

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 Fig. : The diagram shows where some of the most common groups appear on an
infrared spectrum.
This is because a particular group of atoms give rise to characteristic absorption bands in the
IR spectrum, i.e., a particular group strongly absorbs light of certain wavelength in IR
spectrum, no matter to which compound it belongs. For example, IR spectra of both
benzaldehyde and phenyl methyl ketone show pronounced absorption peak at 1,700 cm–1.
This is indicative of the presence of C = O group in both the compounds.

Questions:
1. Distinguish between qualitative and quantitative analysis.
2. What is the purpose of IR spectrometer?
3. Name different forms of electromagnetic wave.
4. Write short note on the electronic transitions caused by energy absorbed in the U.V.
region.
5. Define infrared spectroscopy. Describe the various molecular vibrations in the
technique.
6. Give examples of two applications of each of IR and UV spectroscopy.
7. Give Instrumentation of a spectrophotometer.
8. A compound has a maximum absorbance of 275 nm. ϵ275=8400M−1cm−1 and the path
length is 1 cm. Using a spectrophotometer, if absorbance (A) = 0.70, calculate the
concentration of compound?

Text Book:

1. A Text book of Engineering, Chemistry, P. C. Jain and Monika Jain, 16 th Edition 2013,
Dhanpat Rai Publishing Company (P) LTD, New
2. Engineering Chemistry O. G. Palanna, 1st Edition 2011, Mc Graw Hill, Education (India),
Private Limited, Chennai.
3. A Text book of Engineering, Chemistry S. S. Dara, 1st Edition 2010, S. Chand & Company
Ltd., New Delhi

♦♦♦

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