Instrumental Methods of Analysis

prepared by

Dr. S. M. Nur Alam (Moni)

Associate Professor
Department of Chemical Engineering
Jashore University of Science and Technology

Instrumental Methods of Analysis

Difference between Classical and Instrumental methods

Classical method Instrumental method

Instrumental Methods of Analysis

Spectroscopy is the field of study that measures and interprets
the electromagnetic spectra that result from the interaction
between electromagnetic radiation and matter as a function of
the wavelength or frequency of the radiation.

Instrumental Methods of Analysis

Electromagnetic Radiation
Electromagnetic Radiation
In physics, electromagnetic radiation (EM radiation or EMR) refers to the waves
of the electromagnetic field propagating (radiating) through space, carrying
electromagnetic radiant energy. It includes radio-waves, microwaves, infrared,
visible light, ultraviolet, X-rays, and gamma rays.
Electromagnetic wave can travel through vacuum space
Source of electromagnetic waves

Move them E =0 E E =0 E
vertically
Electric field changing generate magnetic field
Magnetic field changing generate electric field
Electromagnetic waves is transverse wave
Velocity 𝟑 × 𝟏𝟎𝟖 m/s
 Characteristics of electromagnetic radiation
1. These are produced by the oscillation of electric charges and magnetic
field residing on the atom.
2. These are characterized by their wavelengths or frequencies or
wavenumbers.
3. The energy carried by an electromagnetic radiation is directly
proportional to its frequency. The emission or absorption of radiation is
quantized and each quantum of radiation is called a photon.
4. All types of radiations travel with the same velocity and no medium is
required for their propagation. They can travel through vacuum.
5. When visible light ( a group of electromagnetic radiations) is passed
through a prism, it is split up into seven colors which correspond to
definite wavelengths. This phenomenon is called dispersion. Thus, a
group of electromagnetic radiations can be split up into various
components for analysis.
 The electromagnetic spectrum
The arrangement of all types of electromagnetic radiation in order of their increasing
wavelengths or decreasing frequencies is known as complete electromagnetic spectrum.
Wavelength

It is the distance between the two adjacent crests (C-C) or troughs (T-T) in a
particular wave. It is denoted by the letter λ (lamda). It can be expressed in
Angstrom or Nanometer (nm).

Eye can detect only visible light whose wavelength from 3800Å (Violet end) to
7600Å (Red end) while others electromagnetic radiation can not detect.
Wave number
It is the reciprocal of wavelength and it is expressed in per centimeter. In other
words, it is defined as the total number of waves which can pass through a space
of one cm. it is expressed as υ

If the wavelength of a light radiation is known, the corresponding wave number

can be calculated. For example, if the wavelength of a radiation is 2.5 μ, then
the corresponding wave number can be calculated as follows.

λ = 2.5 μ
= 2.5 × 10−4 𝑐𝑚.

1 1
∴ 𝑊𝑎𝑣𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 υ = = −4 = 4000 𝑐𝑚−1
λ 𝑖𝑛 𝑐𝑚 2.5 × 10 𝑐𝑚
Frequency
It is defined as the number of waves which can pass through a point in one second. It
is expressed as υ (nu) in cycles per second or in Hertzs (Hz.) where 1 Hz = 1 cycles
sec-1
1 𝑐
𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 ∝ ; υ=
𝑊𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ λ

Greater the wavelength, smaller is the frequency.

 The wavelength range of visible light is 3800Å-7600Å. The
corresponding frequency range can be calculated as follows:

(a) λ = 3800Å = 3800 × 10−8 cm.

c 2.998 × 1010 cm sec −1

υ= =
λ 3800 × 10−8 cm
= 7.88 × 1014 sec −1

= 7.88 × 1014 Hz = 7.88 × 108 MHz

(b) λ = 7600Å = 7600 × 10−8 cm.

c 2.998 × 1010 cm sec −1

υ= =
λ 7600 × 10−8 cm
= 3.94 × 1014 sec −1

= 3.94 × 1014 Hz = 3.94 × 108 MHz

Energy
The energy of the photon is proportional to the frequency of radiation and is
given by the relationship 𝐸 = ℎυ
Ex 1. Calculate the energy associated with a radiation having wavelength 4000 Å.
Give answer in kcal mole-1 and also in kilo Joules mole-1.

λ = 4000Å = 4000 × 10−8 cm.

c
E = h.
λ
6.628 × 10−27 erg sec × 2.998 × 1010 cm sec −1
=
4000 × 10−8 cm
= 4.968 × 10−12 ergs

4.968 × 10−12 × 6.023 × 1023

=
4.18 × 1010
= 71.6 kcals mole−1
𝐀𝐥𝐬𝐨 𝟏 𝐤𝐜𝐚𝐥 = 𝟒. 𝟏𝟖𝟒 𝐤𝐉
E = 71.6 × 4.134 = 299.5 kJ mole−1
Energy
The energy of the photon is proportional to the frequency of radiation and is
given by the relationship 𝐸 = ℎυ
Ex 1. Calculate the energy associated with a radiation having wavelength 4000 Å.
Give answer in kcal mole-1 and also in kilo Joules mole-1.

λ = 4000Å = 4000 × 10−8 cm.

c
E = h.
λ
6.628 × 10−27 erg sec × 2.998 × 1010 cm sec −1
=
4000 × 10−8 cm
= 4.968 × 10−12 ergs

4.968 × 10−12 × 6.023 × 1023

=
4.18 × 1010
= 71.6 kcals mole−1
𝐀𝐥𝐬𝐨 𝟏 𝐤𝐜𝐚𝐥 = 𝟒. 𝟏𝟖𝟒 𝐤𝐉
E = 71.6 × 4.134 = 299.5 kJ mole−1
Wave and Particle, Dual of Electromagnetic Radiation
According to Plank equation, the energy carryout by photon 𝐸 = ℎν
𝑐
Again, ν = λ, where c is speed of light.

𝑐
∴ 𝐸 = ℎ ⋯⋯⋯ 𝑖
λ
According to Einstein’s equation energy of photon, 𝐸 = 𝑚𝑐 2 ⋯ ⋯ ⋯ 𝑖𝑖
From equation (i) and (ii), 𝑚𝑐 2 = ℎν
ℎν
or, 𝑚𝑐 = 𝑐

Momentum of photon, P = 𝑚𝑐

ℎν
∴𝑃= ⋯ ⋯ ⋯ 𝑖𝑖𝑖
𝑐
ℎ
∴𝑃=
λ
ℎ
∴λ= ⋯ ⋯ ⋯ 𝑖𝑣
𝑃
This is De Broglie wave equation used to describe the wave properties of matter
Ex. 2. Calculate the energy in Joule per quantum calories per mole,
and electron volts of photons of wavelength 𝟑𝟎𝟎𝟎Å.
Solution: We know, 𝐸 = ℎν
𝑐
𝐸=ℎ
λ
−34
Also we know h = 6.62 × 10 𝐽𝑜𝑢𝑙𝑒 − 𝑠𝑒𝑐𝑜𝑛𝑑
𝑐 = 3 × 108 𝑚𝑠 −1
λ = 3000Å = 3000 × 10−8 𝑐𝑚 = 3000 × 10−10 𝑚
Substituting the values of h, c, and λ in above equation, we get
(6.62 × 10−34 𝑗𝑜𝑢𝑙𝑒 − 𝑠𝑒𝑐)(3 × 108 𝑚𝑠 −1 )
𝐸=
3000 × 10−10 𝑚
𝐸 = 6.62 × 10−19 𝐽𝑜𝑢𝑙𝑒
Energy per mole = 𝑁ℎν
Where N= Avogadro’s number = 6.02 × 1023 𝑚𝑜𝑙 −1
Energy per mole = 6.02 × 1023 𝑚𝑜𝑙 −1 6.62 × 10−19 𝑗𝑜𝑢𝑙𝑒
= 3.98 × 105 𝐽𝑜𝑢𝑙𝑒 𝑚𝑜𝑙 −1
3.98 × 105 𝐽𝑜𝑢𝑙𝑒 𝑚𝑜𝑙 −1
=
4.184 𝐽𝑜𝑢𝑙𝑒 𝑐𝑎𝑙 −1
= 95,300 𝑐𝑎𝑙 𝑚𝑜𝑙 −1
95,300 𝑐𝑎𝑙 𝑚𝑜𝑙 −1
=
23,060 𝑐𝑎𝑙 𝑚𝑜𝑙 −1 𝑒𝑉 −1
= 4.13 𝑒𝑉
Ex. 3. Calculate the range in wavelength in nanometers that
corresponds to every transitions of 1.5 to 8.0 eV

Solution: For , 1.5 𝑒𝑉 energy transition,

𝐸 = 1.5 𝑒𝑉 1.6 × 10−12 𝑒𝑟𝑔 𝑒𝑉 = 2.40 × 10−12 𝑒𝑟𝑔.
𝑐
𝐸 = ℎν = ℎ
λ
𝑐
λ =ℎ
𝐸

(6.62 × 10−27 𝑒𝑟𝑔 − 𝑠𝑒𝑐) × (3 × 1010 𝑐𝑚𝑠 −1 )

λ=
2.4 × 10−12 𝑒𝑟𝑔.

= 8.25 × 10−5 𝑐𝑚
= 825 𝑛𝑚
 Spectroscopy
Spectroscopy is the branch of science dealing with the study of interaction of
electromagnetic radiation with matter. The most important consequence of such
interaction is that energy is absorbed or emitted by the matter in discrete amounts
called quanta.
The study of spectroscopy can be carried out under the following heads:
1. Atomic Spectroscopy: This deals with the interaction of electromagnetic
radiations with atoms which are most commonly in their lowest energy state
called the ground state.
2. Molecular spectroscopy: This deals with the interaction of electromagnetic
radiation with molecules. The results in transitions between rotational and
vibrational energy levels in additions to electronic transitions. As a results, the
spectra of molecules are much more complicated than those of atoms.
i. Rotational (Microwave) Spectra
ii. Vibrational and Vibrational-Rotational (Infrared) Spectra
iii. Raman Spectra
iv. Electronic Spectra
v. Nuclear Magnetic Resonance (NMR)
vi. Electron Spin Resonance (ESR)
vii. Mossbauer Spectra (also called Nuclear Gamma Resonance
Fluorescence (NRF) spectra
 Instrumental Methods of Chemical Analysis
In the broader sense, an instrument for chemical analysis does not generate
quantitative data but instead simply converts chemical information to a form that is
more readily observable. Thus, the instrument can be visualized as a
communication device. The various steps perform with instrument as follows:

I. Generation of a signal: The signal uses in the instrument may be produced

from the sample itself

II. Transduction: The transformation of a signal to one of a different nature is

called transduction.

III. Amplification of the transformed signal: It is possible to increase the

sensitivity of many instruments by amplification of the original signal or its
transduced form.

IV. Presentation of the Signal: The transduced and amplified signal from an
instrument is generally presented as a linear or angular displacement along a
scale.
 Classification of Instrumental Methods

Physical property measured Instrumental methods based on

measurement of property
Absorption of radiation Spectrophotometry, such as X-ray, UV-Vis
Emission of radiation Emission spectroscopy such as X-ray, UV
Scattering of radiation Raman spectroscopy
Refraction of radiation Refractometry
Diffraction of radiation X-ray diffraction
Rotation of radiation Polarimetry
Electrical Potential Potentiometry
Electrical conductance Conductivity
Electric current Polargraphy
Quantity of electricity Coulometry
Mass-to-charge ratio Mass spectroscopy
Thermal properties Thermal conductivity
Principle Applications of Analytical Techniques

1. Molecular Analysis
I. Nuclear magnetic resonance
II. Infrared spectroscopy
III. Ultraviolet-visible spectroscopy
IV. X-ray diffraction
V. Mass spectroscopy
VI. Thermal analysis
VII. Chromatography

2. Elemental Analysis
I. Atomic absorption spectroscopy
II. Emission spectroscopy
III. X-ray fluorescence
IV. Electron spectroscopy for chemical analysis