UNIT-2 Spectroscopic Techniques and Applications

Question Bank

Part-A

1. Define Spectroscopy.
Spectroscopy is the study of the interaction between matter and
electromagnetic radiation.
2. Write the differences between atomic and molecular spectroscopy.

3. What are absorption and emission spectroscopy?

4. Write the criteria for any molecule to be “Microwave active”.
The condition for a molecule to be microwave active is to be Polar and
should have a permanent dipole moment. There are various molecules that
are molecule active
5. Among the following molecules, predict which are microwave active? H2,
Cl2, HCl, H2O.
6. Name any two examples of asymmetric, spherical and symmetric top
molecules.

7. What is the selection rule and principle of rotational spectroscopy?

A molecule must have a transitional dipole moment that is in resonance with
an electromagnetic field for rotational spectroscopy to be
used. Polar molecules have a dipole moment. A transitional dipole moment
not equal to zero is possible.
Selection rule : ΔJ = ± 1
 Rotational spectroscopy is concerned with the measurement of the energies
of transitions between quantized rotational states of molecules in the gas
phase. The spectra of polar molecules can be measured in absorption or
emission by microwave spectroscopy.

8. What is the principle and selection rule for vibrational spectroscopy?

The selection rule for a harmonic oscillator transition is ∆v = ± 1.

9. What are fundamental absorptions in vibrational spectroscopy?
Fundamental vibrational frequencies of a molecule corresponds to
transition from v=0 to v=1. For a non-linear molecule there will by 3N-6
(where N is the number of atoms) number vibrations.
10.What do you mean by finger-print region? Write its significances.
 The region to the right-hand side of the diagram (from about 1500 to 500
cm-1) usually contains a very complicated series of absorptions.
These are mainly due to all manner of bending vibrations within the
molecule. This is called the fingerprint region.
11.Write the selection rules for electronic spectroscopy.
The Selection Rules governing transitions between electronic energy
levels of transition metal complexes are: ΔS = 0 The Spin Rule. Δl = +/- 1.
12.What are chromophores and auxochromes?
An auxochrome is a functional group of atoms attached to
the chromophore which modifies the ability of the chromophore to absorb
light, altering the wavelength or intensity of the absorption.
A chromophore is the part of a molecule responsible for its color. ...
Visible light that hits the chromophore can thus be absorbed by exciting an
electron from its ground state into an excited state.
13.What is Raman scattering?
When light is scattered by matter, almost all of the scattering is an
elastic process (Rayleigh scattering) and there is no change in energy.
However, a very small percentage of scattering is an inelastic process, thus a
scattered light has different energy from incident light. is called Raman
scattering (Raman effect).

14.What is Stokes and anti-Stokes shifts?

 A few part of scattered light has lower frequencies (higher wavelengths)
than incident light, given origin to the Stokes lines in a Raman spectrum.
This occurs when a photon transfer part of its energy to the molecule and,
since it loses energy, its frequency is shifted towards lower frequencies.
It is possible to the molecule transferring energy to the incident
photon and shifting frequency of scattered light to higher values (lower
wavelengths). When this occurs, the molecule that is in excited vibrational
state undergoes transition to the lower state or even to the ground state. A set
of lines appears in a Raman spectrum (anti-Stokes lines).

15.What is diffraction of light?

Diffraction is the slight bending of light as it passes around the edge of an
object. The amount of bending depends on the relative size of the
wavelength of light to the size of the opening. If the opening is much larger
than the light's wavelength, the bending will be almost unnoticeable.

16.What is X-ray diffraction?

X-ray diffraction, a phenomenon in which the atoms of a crystal, by virtue
of their uniform spacing, cause an interference pattern of the waves present
in an incident beam of X rays. The atomic planes of the crystal act on the X
rays in exactly the same manner as does a uniformly ruled grating on
a beam of light.
17.State the mutual exclusion principle of Raman spectroscopy for CO2.
 Part-B

1. With a neat sketch explain the regions of electromagnetic spectrum.

2. a) State the selection rule for rotational spectroscopy and with a neat
diagram

Selection rules
Only those transitions are allowed for which ∆J=+1 or -1
Transitions between rotational states can be observed in molecules with a
permanent electric dipole moment
Classification of molecular rotors
Spherical tops (spherical rotors) All three moments of inertia are equal to
each other: IA = IB = IC. Examples of spherical tops include phosphorus
tetramer (P4), carbon tetrachloride (CCl4)

Linear molecules. For a linear molecule the moments of inertia are related
by IA << IB = IC . dinitrogen, N

Symmetric tops (symmetric rotors) A symmetric top is a molecule in which

two moments of inertia are the same, IA=IB, IA= IB. By definition a
symmetric top must have a 3-fold or higher order rotation axis. Examples of
symmetric tops include
Oblate: benzene, C6H6
Asymmetric tops (asymmetric rotors) The three moments of inertia have
different values. Examples of small molecules that are asymmetric tops
include water, H2O and nitrogen dioxide, NO
 b) Discuss in detail the applications of Microwave spectroscopy.
• Rotational spectroscopy has primarily been used to investigate fundamental
aspects of molecular physics. It is a uniquely precise tool for the
determination of molecular structure in gas phase molecules.
• It can be used to establish barriers to internal rotation such as that associated
with the rotation of the CH3 group relative to the C6H4Cl group in
chlorotoluene (C7H7Cl).
• When fine or hyperfine structure can be observed, the technique also
provides information on the electronic structures of molecules.
• Much of current understanding of the nature of weak molecular interactions
such as van der Waals, hydrogen and halogen bonds has been established
through rotational spectroscopy.
• In connection with radio astronomy, the technique has a key role in
exploration of the chemical composition of the interstellar medium.
• Microwave transitions are measured in the laboratory and matched to
emissions from the interstellar medium using a radio telescope.
 • NH3 was the first stable polyatomic molecule to be identified in the
interstellar medium.
• The measurement of chlorine monoxide is important for atmospheric
chemistry. Current projects in astrochemistry involve both laboratory
microwave spectroscopy and observations made using modern
radiotelescopes such as the Atacama Large Millimetre Array

3. a) With a neat sketch, explain the vibrational spectra of molecules.

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) involves
the interaction of infrared radiation with matter. It covers a range of
techniques, mostly based on absorption spectroscopy.
Number of vibrational modes
In order for a vibrational mode in a sample to be "IR active", it must
be associated with changes in the dipole moment. A permanent dipole is not
necessary, as the rule requires only a change in dipole moment.

A molecule can vibrate in many ways, and each way is called a

vibrational mode. For molecules with N number of atoms, linear molecules
have 3N – 5 degrees of vibrational modes, whereas nonlinear molecules
have 3N – 6 degrees of vibrational modes (also called vibrational degrees of
freedom). As an example H2O, a non-linear molecule, will have 3 × 3 – 6 =
3 degrees of vibrational freedom, or modes.
 Simple diatomic molecules have only one bond and only one
vibrational band. If the molecule is symmetrical, e.g. N2, the band is not
observed in the IR spectrum, but only in the Raman spectrum. Asymmetrical
diatomic molecules, e.g. CO, absorb in the IR spectrum. More complex
molecules have many bonds, and their vibrational spectra are
correspondingly more complex, i.e. big molecules have many peaks in their
IR spectra.

The atoms in a CH2X2 group, commonly found in organic

compounds and where X can represent any other atom, can vibrate in nine
different ways. Six of these vibrations involve only the CH2 portion:
symmetric and antisymmetric stretching, scissoring, rocking, wagging and
twisting, as shown below. Structures that do not have the two additional X
groups attached have fewer modes because some modes are defined by
specific relationships to those other attached groups. For example, in water,
the rocking, wagging, and twisting modes do not exist because these types of
motions of the H represent simple rotation of the whole molecule rather than
vibrations within it.
infrared (IR) spectroscopy is a measurement technique that allows one
to record infrared spectra. Infrared light is guided through an interferometer
and then through the sample (or vice versa). A moving mirror inside the
apparatus alters the distribution of infrared light that passes through the
interferometer. The signal directly recorded, called an "interferogram",
represents light output as a function of mirror position. A data-processing
technique called Fourier transform turns this raw data into the desired result
(the sample's spectrum): Light output as a function of infrared wavelength
(or equivalently, wavenumber). As described above, the sample's spectrum
is always compared to a reference.
b) Explain in detail the applications of Infra Red spectroscopy.

Application of IR Spectroscopy
 iv. Determination of shape molecules
Linear Shape (3n-5) Ex: O=C=O
Bend shape (3n-6) Ex: H2O

v. Determination of molecular weight

vi. Crystallinity

vii. Determination of aromaticity

Frequency value for C-H bond aliphatic is 1400cm-1
But in aromatic compound frequency of C-H bond is
observed in range of 3100 cm-1

viii. Determination of hydrogen bonding

➢ Intermolecular hydrogen bonding (b/w molecules)
➢ Intramolecular hydrogen bonding (within molecules)

• Intermolecular hydrogen
bonding disappear on
dilution.

• Intramolecular hydrogen
bonding is stable even at
very dilute conditions.

4. Discuss about the X-ray diffraction of light by Bragg equation.

X-ray diffraction, a phenomenon in which the atoms of a crystal, by virtue
of their uniform spacing, cause an interference pattern of the waves present
in an incident beam of X rays. The atomic planes of the crystal act on the X
rays in exactly the same manner as does a uniformly ruled grating on a beam
of light.
Bragg law, in physics, the relation between the spacing of atomic planes
in crystals and the angles of incidence at which these planes produce the
most intense reflections of electromagnetic radiations, such as X rays and
gamma rays, and particle waves, such as those associated with electrons and
neutrons.
The diagram shows waves 1 and 2, in phase with each other, glancing
off atoms A and B of a crystal that has a separation distance d between its
atomic, or lattice, planes. The reflected (glancing) angle θ, as shown by
experiment, is equal to the incident angle θ. The condition for the two waves
to stay in phase after both are reflected is that the path length CBD be a
whole number (n) of wavelengths (λ), or nλ. But, from geometry, CB and
BD are equal to each other and to the distance d times the sine of the
reflected angle θ, or d sin θ.
Thus, nλ = 2d sin θ
5. a) Draw and explain the energy level diagram in UV-Visible spectroscopy.
 Fig. Electronic energy level diagram

b) Write a detailed note on the applications of UV-Visible spectroscopy.

UV/Vis spectroscopy is routinely used in analytical chemistry for the
quantitative determination of different analytes, such as transition metal
ions, highly conjugated organic compounds, and biological macromolecules.
Spectroscopic analysis is commonly carried out in solutions but solids and
gases may also be studied.

Solutions of transition metal ions can be colored (i.e., absorb visible

light) because d electrons within the metal atoms can be excited from one
electronic state to another. The colour of metal ion solutions is strongly
affected by the presence of other species, such as certain anions or ligands.
For instance, the colour of a dilute solution of copper sulfate is a very light
blue; adding ammonia intensifies the colour and changes the wavelength of
maximum absorption (λmax).
Organic compounds, especially those with a high degree of
conjugation, also absorb light in the UV or visible regions of the
electromagnetic spectrum. The solvents for these determinations are often
water for water-soluble compounds, or ethanol for organic-soluble
compounds. (Organic solvents may have significant UV absorption; not all
solvents are suitable for use in UV spectroscopy. Ethanol absorbs very
weakly at most wavelengths.) Solvent polarity and pH can affect the
 absorption spectrum of an organic compound. Tyrosine, for example,
increases in absorption maxima and molar extinction coefficient when pH
increases from 6 to 13 or when solvent polarity decreases.
While charge transfer complexes also give rise to colours, the colours
are often too intense to be used for quantitative measurement.
The Beer–Lambert law states that the absorbance of a solution is
directly proportional to the concentration of the absorbing species in the
solution and the path length. Thus, for a fixed path length, UV/Vis
spectroscopy can be used to determine the concentration of the absorber in a
solution. It is necessary to know how quickly the absorbance changes with
concentration. This can be taken from references (tables of molar extinction
coefficients), or more accurately, determined from a calibration curve.

A UV/Vis spectrophotometer may be used as a detector for HPLC.

The presence of an analyte gives a response assumed to be proportional to
the concentration. For accurate results, the instrument's response to the
analyte in the unknown should be compared with the response to a standard;
this is very similar to the use of calibration curves. The response (e.g., peak
height) for a particular concentration is known as the response factor.

6. What is Raman Effect? With a neat sketch describe the quantum theory
of Raman Effect.

When light is scattered by matter, almost all of the scattering is an

elastic process (Rayleigh scattering) and there is no change in energy.
However, a very small percentage of scattering is an inelastic process, thus a
scattered light has different energy from incident light is called Raman
scattering (Raman effect).
 When a monochromatic light is scattered by molecules, most of emerging
light has the same frequency of the incident light; this process is called Rayleigh
scattering.

A few part of scattered light has lower frequencies (higher wavelengths)

than incident light, given origin to the Stokes lines in a Raman spectrum. This
occurs when a photon transfer part of its energy to the molecule and, since it loses
energy, its frequency is shifted towards lower frequencies. The molecule absorbs
energy to undergo transition to higher vibrational states.

It is possible to the molecule transferring energy to the incident photon and

shifting frequency of scattered light to higher values (lower wavelengths). When
this occurs, the molecule that is in excited vibrational state undergoes transition to
the lower state or even to the ground state. A set of lines appears in a Raman
spectrum (anti-Stokes lines), owing to this process.

A typical Raman spectrum is centered at the frequency of incident light

(normally a laser in the visible part of spectrum), with very high intensity owing to
Rayleigh scattering. Stokes lines can be seen towards lower frequencies and anti-
Stokes towards higher frequencies, like then are mirrored at the center of the
spectrum. Nevertheless, Stokes lines are more intense than their anti-Stokes
counterparts, because vibrational ground state is more populated than excited
states.

7. Discuss in detail the applications of Raman Spectroscopy

Note: Write application of IR spectroscopy here.

Just replace the name: Raman spectra instead of IR spectra

8. Explain the Franck-Condon Principle of UV Spectrum.

The Franck-Condon Principle describes the intensities of vibronic
transitions, or the absorption or emission of a photon. It states that
when a molecule is undergoing an electronic transition, such as
ionization, the nuclear configuration of the molecule experiences no
significant change.
This is due in fact that nuclei are much more massive than
electrons and the electronic transition takes place faster than the nuclei
can respond. When the nucleus realigns itself with with the new
electronic configuration, the theory states that it must undergo a
vibration.
If we picture the vertical transition from ground to excited
electronic state as occurring from a vibrational wave function that gives
a probability distribution of finding the nuclei in a give region of space
we can determine the probability of a given vibrational level from the
overlap integral, which gives the overlap of the vibrational wave
function in the ground and excited state. The transition probability can
be separated into electronic and nuclear parts using the Condon
approximation
Figure: Franck–Condon principle energy diagram.