Module IV

Analytical Techniques for Engineers

Electromagnetic Radiation
Spectroscopy Energy levels
 UV Spectroscopy
Molecular spectroscopy that involves study of the interaction of Ultraviolet (UV)-Visible
radiation with molecules.
Ultraviolet light and visible light have just the right energy to cause an electronic
Transition of electron from one filled orbital to another of higher Energy unfilled orbital
When a molecule absorbs light of an appropriate wavelength and an electron is
promoted to a higher energy molecular orbital, the molecule is then in an excited state.
The Wavelength of absorbed light will provide the information on the energy gap which
is related to functional group.

UV Spectrum of Acetone
UV Spectroscopy
UV Spectroscopy
 UV Spectroscopy
Beer–Lambert law: At a given wavelength, absorption is proportional to the
concentration of absorbing molecules and the path length of the light through the
sample
A = absorbance of the sample
I0 = intensity of the radiation entering the sample
I = intensity of the radiation emerging from the sample
l = length of the light path through the sample, in centimeters
c = concentration of the sample, in moles/liter
ε = molar absorptivity (L mol-1 cm-1 or M-1 cm-1 ) where M = mol L-1

The molar absorptivity (formerly called the extinction coefficient) of a compound is a

constant that is characteristic of the compound at a particular wavelength
Molar absorptivities may be very large for strongly absorbing compounds ( >10,000)
and very small if absorption is weak ( = 10 to 100) No absorption gives ε = 0!
UV Spectroscopy
UV Spectroscopy
UV Spectroscopy
 UV Spectroscopy

The sensitivity of detection of the light beam after it passes through the sample is
high since it uses a non-split light beam (therefore, high energy exists
throughout). Single beam spectrophotometers are available in analysis at visible
and ultraviolet wavelength ranges.

A single beam spectrophotometer measures the concentration of an analyte in a

sample by measuring the amount of light absorbed by that analyte. Here, the Beer
Lambert Law comes into operation. This law states that the concentration of an
analyte is directly proportional to the absorbance.
UV Spectroscopy
UV Spectroscopy
UV Spectroscopy
 IR Spectroscopy
It is the spectroscopy which deals with the infrared region (700 nm to 1000 μm) of the electromagnetic
spectrum with a longer wavelength and lower frequency than visible light.
Principle
IR spectra is produced by the absorption of energy by a molecule in the infrared region and the transitions
occur between vibrational levels. Hence IR spectroscopy is also known as vibrational spectroscopy It is
divided into three regions.
(i) Near IR – 12500 to 4000 cm-1
(ii) MID IR – 4000 to 400 cm-1 N
(iii) Far IR – 400 to 50 cm-1 E
A
The most useful IR region lies between 4000 to 400 cm-1
R
Theory of IR absorption
IR radiation does not have sufficient energy to induce electronic transitions like M
UV-Visible spectroscopy. It causes only vibrational and rotational changes.

infrared
I
For a molecule to absorb IR radiation, two conditions must be satisfied. D
(i) There must be change in the net dipole moment of the molecule during the
F
vibration.
A
(i) The energy of the IR radiation must match the energy difference between R
two vibrational levels.
The bonds of a molecule experience various types of vibrations. The atoms are not
stationary and fluctuate continuously. Vibrational motions are defined by stretching
and bending modes. There are two types of vibrations.
(i) Stretching Vibration – Symmetric and Asymmetric
(ii) Bending Vibration – (a) Inplane bending – Rocking, Scissoring,
(b) Outplane bending – Wagging and Twisting.
IR Spectroscopy
 IR Spectroscopy

Instrumentation - Block diagram of IR spectrophotometer

IR Spectroscopy
 IR Spectroscopy - Application
Identification of functional group and structure elucidation
Entire IR region is divided into group frequency region and fingerprint region. Range of group frequency is
4000-1500 cm-1 while that of finger print region is 1400-600 cm-1. In group frequency region, the peaks
corresponding to different functional groups can be observed. According to corresponding peaks, functional
group can be determined. Each atom of the molecule is connected by bond and each bond requires different
IR region so characteristic peaks are observed. This region of IR spectrum is called as finger print region of
the molecule. It can be determined by characteristic peaks.
Identification of substances: IR spectroscopy is used to establish whether a given sample of an organic
substance is identical with another or not. This is because large number of absorption bands is observed in
the IR spectra of organic molecules and the probability that any two compounds will produce identical
spectra is almost zero. So if two compounds have identical IR spectra then both of them must be samples of
the same substances. IR spectra of two enatiomeric compound are identical. So IR spectroscopy fails to
distinguish between enantiomers. For example, an IR spectrum of benzaldehyde is observed as follows.
C-H stretching of aromatic ring- 3080 cm-1
C-H stretching of aldehyde- 2860 cm-1 and 2775 cm-1
C=O stretching of an aromatic aldehyde - 1700 cm-1
C=C stretching of an aromatic ring- 1595 cm-1
C-H bending - 745 cm-1 and 685 cm-1
Studying the progress of the reaction: Progress of chemical reaction can be determined by examining the
small portion of the reaction mixure withdrawn from time to time. The rate of disappearance of a
characteristic absorption band of the reactant group and/or the rate of appearance of the characteristic
absorption band of the product group due to formation of product is observed.
Detection of impurities: IR spectrum of the test sample to be determined is compared with the standard
compound. If any additional peaks are observed in the IR spectrum, then it is due to impurities present in
the compound.
IR Spectroscopy
IR Spectroscopy
Nuclear Magnetic Resonance
 Nuclear Magnetic Resonance
The simplest nucleus is that of the hydrogen atom, which consists of one particle
only, the proton. The protonic mass and charge are taken as the units of atomic
mass and charge, respectively. The charge is equal in magnitude but opposite in
sign to the electronic charge. The proton also has a spin of ½.

Another particle is the neutron (apart from the hydrogen nucleus). It has no
charge and has spin of ½.

Spin of a electron = ½ and the angular momentum =

Consider a nucleus having ‘p’ protons and ‘n’ neutrons.

Total mass = p + n (ignoring the nuclear binding energy)
Total charge = + p
Total spin = vector combination of p + n spins each of magnitude ½.

Observed spins can be rationalized and some empirical rules have been
formulated.

Spin of a nucleus (I) and its angular momentum I = I (I +1)

12C – 6 protons and 6 neutrons

13C – 6 protons and 7 neutrons – will have its own spin value.
 Nuclear Magnetic Resonance

Spin of a nucleus (I) and

its angular momentum I = I (I +1)

No. of Protons No. of Neutrons Total mass Total Spin of Example

charge nucleus (I)
4He, 12C,
Even Even Even Even Zero
16O

Odd Odd Even Odd Integral 2H (I = 1),

spin 14N (I = 1),
10B (I = 3)

Even Odd Odd Odd/Even Half- 1H, 13C,

Odd Even integral 15N

spin (I = 1/2)
Principle - NMR

They are degenerate

In presence of magnetic field.

Principle - NMR
Principle - NMR
 Principle - NMR
Larmor Frequency
One of the beautiful features of spins in a magnetic field is that they can not
be aligned exactly in the field direction but precess in a cone around the field
axis
 Principle - NMR

An implication is that soon after absorbing radio frequency, the population of the lower
and upper levels becomes equal (ie, the system is saturated) and then there is no more
absorption. In these methods, the nuclei absorb radiation and relax to the lower levels
several times in the given pulse sequence of an experiment.
 NMR Hydrogen Nuclei
When placed in a magnetic field, the surrounding electron cloud tends to circulate
in such a direction as to produce a field opposing that applied. The total field
experienced by the nucleus is

σ is called the shielding constant.

Different environments have different shielding constants because the
electron densities at different protons (such as a methyl proton, an
acetylenic proton, a hydroxyl proton, etc) are different.
 NMR - Chemical Shift
Chemical shift: the exact field strength (in ppm) of a nuclei comes into
resonance relative to a reference standard. To develop a chemical shift scale,
we need a reference compound. Tetramethylsilane (TMS, i.e., Si(CH3)4) which
has 12 equivalent protons and has a sharp resonance at high field is used as
a reference.
NMR – Spin-Spin Coupling
NMR – Spin-Spin Coupling

R-CH(OH)-CH2-CH(R)-Br
CH3-CH2-CH2-COOH
C6H5-CH2-CH3
 NMR – Summary

• The area of an absorption peak is proportional to the number of

equivalent nuclei