Name: DIBYAJYOTI DEY

Roll No.: 18145070

Branch: Metallurgical Engineering [ 3rd Year, B. Tech]
MT-322: Instrumental Analysis
Mid Term Examination 2020-21

PART-A
Q1. Define qualitative and quantitative analysis.

A: Most analyses are carried out by separating the components of interest (the analytes) in
a sample by precipitation, extraction, or distillation. Then these analytes can be analysed
both qualitatively and quantitatively.
Qualitative Analysis: The analytes are first treated with reagents to yield products that can
then be recognized and classified by their colours, their boiling or melting points, their
solubilities in a series of solvents, their odours, their optical activities, or their refractive
indexes. These classifications are then used to make qualitative conclusions about the
nature and other characteristics of the sample in question.
Quantitative Analysis: It is a technique that uses mathematical and statistical modelling,
measurement, and research to understand the behaviour and characteristics of the sample
in question.
For e.g., in gravimetric measurements, the mass of the analyte or some compound
produced from the analyte is determined. In volumetric, also called titrimetric, procedures,
the volume or mass of a standard reagent required to react completely with the analyte is
measured.
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Q2. Explain two postulates of Quantum Theory proposed by Max Plank.

A: The quantum theory was first proposed in 1900 by Max Planck, a German physicist, to
explain the properties of radiation emitted by heated bodies. The theory was later
extended to rationalize other types of emission and absorption processes.

Two important postulates of Quantum theory include the following:

1. Atoms, ions, and molecules can exist only in certain discrete states, characterized by
definite amounts of energy. When a species changes its state, it absorbs or emits an
amount of energy exactly equal to the energy difference between the states.
 2. When atoms, ions, or molecules absorb or emit radiation in making the transition
from one energy state to another, the frequency, ν or the wavelength, λ of the
radiation is related to the energy difference between the states by the equation

E1 – E0 = hν = hc/ λ
where E1 is the energy of the higher state and E0 the energy of the lower state.
The terms c and h are the speed of light and the Planck constant, respectively.

For atoms or ions in the elemental state, the energy of any given state arises from
the motion of electrons around the positively charged nucleus. As a consequence,
the various energy states are called electronic states. In addition to having electronic
states, molecules also have quantized vibrational states that are associated with the
energy of interatomic vibrations and quantized rotational states that arise from the
rotation of molecules around their centres of mass.

The lowest energy state of an atom or molecule is its ground state. Higher energy
states are termed excited states. Generally. at room temperature chemical species
are in their ground state.
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Q3. What are the different ways of excitation for emission of electromagnetic
radiation? Mention the types of emitted radiations in each case.

A: Electromagnetic radiation is produced when excited particles (atoms, ions, or molecules)

relax to lower energy levels by giving up their excess energy as photons. Excitation can be
brought about by a variety of means. Including

1. bombardment with electrons or other elementary particles, which generally leads to

the emission of X-radiation;
2. exposure to an electric current, an AC spark, or an intense heat source (flame, DC arc,
or furnace), producing ultraviolet, visible, or infrared radiation;
3. irradiation with a beam of electromagnetic radiation, which produces fluorescence;
4. an exothermic chemical reaction that produces chemiluminescence.
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Q4. Describe components for an emission spectrometer with functions of

each component in brief.
A: All emission spectrometers share 3 common components even if they operate in
different spectral regions, namely:
• Light Source
• Filters
• Monochromator
• Radiation detector
Now, let’s discuss them in detail one by one,
1. Light source
Radiation sources are usually classified as broadband sources or line sources.

Broadband sources emit a continuous spectrum, as their name would indicate, over a
wide range of wavelengths.

Line sources, on the other hand, are those in which the emitted radiation arises from
specific transitions within atoms of a certain element which are stimulated to emit by
being excited electrically or thermally.

2. Filters
Now from the light source a narrow beam of wavelength has to be isolated for
measurement so we have filters for that purpose.

Absorption filters are made of a variety of materials such as gelatine, plastic, or glass.
These are designed to scatter or absorb light of wavelengths higher or lower than their
cut-off wavelength. Two of these, one to remove short wavelengths and one to remove
higher wavelengths, can serve to allow only a narrow band of wavelengths to pass.
These filters can be used for narrow band passes.

Interference filters work on the principle that light beams will interfere either
constructively or destructively, if they are in phase or out of phase with each other.
These are constructed from two half-silvered mirrored surfaces held apart by a
transparent spacer that is an integer number (1, 2, or 3) of half wavelengths in thickness.
These filters give a narrow bandpass of 10-15 nm. The most common or reinforced
frequency is given by:
f = 2𝛍b/m
𝛍: refractive index of transparent spacer, m: order of filter, b: thickness of spacer

3. Monochromators
When a filter is not adequate, for instance when it is desired to make measurements at
discrete wavelengths over a span of wavelengths, one must use a monochromator. This
is a device that takes the incident polychromatic radiation and spreads it out in space.
Different wavelengths of light are thus directed to different points.

The monochromator consists of:

(a) the dispersing device, usually a grating for the range from the ultraviolet through the
infrared,
(b) a means of adjusting the angles between the incident beams, the dispersing device
and the detector,
(c) optics as focusing lenses, collimators and mirrors which keep the light traveling in
organized beams through the monochromator.
 4. Detectors:
A detector is necessary to measure either radiation produced by the sample in emission
or fluorescence or the radiation transmitted through the sample in absorbance
spectroscopic methods.

Qualities to be sought in a detector are usually a sensitive response to radiation over a

reasonably wide wavelength range, as well as stability, and low noise. Gain and response
time will also have a significant effect on the use of the detector.

The signals arising from these devices are often very small, and may require substantial
amplification. In some detectors, several sensing elements may be joined to provide a
larger signal. All detectors produce current or voltage signals which may be subject to
some noise or drift. To improve the signal to noise ratio of these devices, the signal is
usually modulated into an AC signal.
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Q5. What are the basic components in a monochromator?

A: For many spectroscopic methods, it is necessary or desirable to be able to continuously

vary the wavelength of radiation over a broad range. This process is called scanning (a
spectrum. Monochromators are designed for spectral scanning. Monochromators for
ultraviolet, visible, and infrared radiation arc all similar in mechanical construction in the
sense that they use slits, lenses, mirrors, windows, and gratings or prisms. The materials
from which these components are fabricated depend on the wavelength region of intended
use.

Components of Monochromators:
1. an entrance slit that provides a rectangular optical image,
2. a collimating lens or mirror that produces a parallel beam of radiation,
3. a prism or a grating that disperses the radiation into its component wavelengths,
4. a focusing element that reforms the image of the entrance slit and focuses it on a
planar surface called a focal plane, and
5. an exit slit in the focal plane that isolates the desired spectral band. In addition, most
monochromators have entrance and exit windows designed to protect the
components from dust and corrosive laboratory fumes.

Below are the 2 types of popular monochromators:

(a) Czerney -Tumer grating monochromator

(b) Bunsen prism monochromator
(In both instances, λ1 > λ2)
 _________________________

Q6. Explain the functioning of photo-multiplier tube.

A: For the measurement of low radiant powers, the photomultiplier tube (PMT) offers
advantages over an ordinary phototube, the photocathode surface emits electrons when
exposed to radiation. The tube also contains additional electrodes called dynodes.

Dynode 01 is maintained at a voltage approximately 90 V more positive than the cathode,

and electrons are accelerated toward it as a result. Each photoelectron that strikes the
dynode causes emission of several additional electrons. These electrons, in turn, are
accelerated toward dynode 02, which is ~90 V more positive than dynode 01.

Again, several electrons are emitted for each electron that strikes the surface. By the time
this process has been repeated nine times, 106 to 107 electrons have been formed for each
incident photon. This cascade of electrons is finally collected at the anode and the resulting
current is then converted to voltage and measured.

Photomultipliers are highly sensitive to ultraviolet and visible radiation. In addition, they
have extremely fast response times.

Photomultiplier tubes are limited to measuring low power radiation because intense light
causes irreversible damage to the photoelectric surface. For this reason, the device is
always housed in a light-tight compartment and care is taken to eliminate the possibility of
its being exposed even momentarily to daylight or other strong light while powered. With
appropriate external circuitry, photomultiplier tubes can be used to detect the arrival of
individual photons at the photocathode.

Photomultiplier tube: (a) photograph of a typical commercial tube; (b) cross: sectional view; (c) electrical diagram
illustrating dynode polarization and photocurrent measurement.

Spectral response of some typical photo-emissive surfaces

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Q7. Explain the functioning of a silicon photodiode transducer.

A: A silicon photodiode transducer consists of a reverse biased p-n junction formed on a

silicon chip. The reverse bias creates a depletion layer that reduces the conductance of the
junction to nearly zero.
If radiation impinges on the chip, however, holes and electrons are formed in the depletion
layer and swept through the device to produce a current that is proportional to radiant
power. They require only low-voltage power supplies or can be operated under zero bias
and so can be used in portable, battery-powered instruments.

Silicon diodes are more sensitive than vacuum phototubes but less sensitive than
photomultiplier tubes. Photodiodes have spectral ranges from about 190 to 1100 nm.
_________________________

Q8. Explain the underlying principle of Atomic Absorption Spectrometry.

A: In analytical chemistry the technique is used for determining the concentration of a

particular element (the analyte) in a sample to be analysed. AAS can be used to determine
over 70 different elements in solution, or directly in solid samples via electrothermal
vaporization, and is used in pharmacology, biophysics, archaeology and toxicology research.

Principle
The technique makes use of the atomic absorption spectrum of a sample in order to assess
the concentration of specific analytes within it.
It utilizes the fact that elements in the gas phase absorb very specific wavelengths. The
analyte absorbs specific wavelength and transits to a higher state. The amount of
absorption gives the concentration. It requires standards with known analyte content to
establish the relation between the measured absorbance and the analyte concentration
and relies therefore on the Beer-Lambert law:

A=𝛆IC
where, 𝛆 = absorptivity, l = optical path length, C=concentration
Concentration measurements are usually determined by a working curve made after
calibrating the instrument as per the standards.
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Q9. Explain the functioning of a hollow cathode lamp as a source of radiation

in AAS.

A: The most common source for atomic absorption measurements is the hollow-cathode
lamp.

This type of lamp consists of a tungsten anode and a cylindrical cathode sealed in a glass
tube filled with neon or argon at a pressure of 1 to 5 torr.
The cathode is constructed of the metal whose spectrum is desired or serves to support a
layer of that metal.

Functioning
1. Ionization of the inert gas occurs when a potential difference on the order of 300 V is
applied across the electrodes, which generates a current of about 5 to 15 mA as ions
and electrons migrate to the electrodes.
2. If the voltage is sufficiently large, the gaseous cations acquire enough kinetic energy
to dislodge some of the metal atoms from the cathode surface and produce an
atomic cloud in a process called sputtering.
3. A portion of the sputtered metal atoms are in excited states and thus emit their
characteristic radiation as they return to the ground state.
4. Eventually, the metal atoms diffuse back to the cathode surface or to the glass walls
of the tube and are redeposited.

Efficiency Factors
1. Geometry:
The cylindrical configuration of the cathode tends to concentrate the radiation in a
limited region of the metal tube; this design also enhances the probability that
redeposition will occur at the cathode rather than on the glass walls
 2. Operating voltage:
This advantage is overridden somewhat by an increase in Doppler broadening of the
emission lines from the lamp.
Furthermore, the greater currents produce an increased number of unexcited atoms in
the cloud. The unexcited atoms, in turn, are capable of absorbing the radiation emitted
by the excited ones. This self-absorption leads to lowered intensities, particularly at the
centre of the emission band.
_________________________

Q10. Convert the following percent transmittance data into absorbance:

a.29.9 b.86.1

A: Absorbance is a negative log of transmittance, here we are given transmittance

percentages.
A = - log(T)
(a) Given, T = 29.9%,
Therefore, A = - log (29.9/100) [percentage value to actual value]
or, A = 0.524. [Ans]

(b) Given, T = 86.1%,

Therefore, A = - log (86.1/100) [percentage value to actual value]
or, A = 0.065 [Ans]

[End of Part A. Scroll down for Part B]

 PART-B
The correct options are highlighted with green and also been ticked

Q1. In emission spectrometry, the power of radiation is

√ i) Directly proportional to the electrical signal produced by transducer
ii) Directly proportional to the analyte concentration
iii) Both of the above

Q2. In inductively coupled plasma source the tesla coil is used for
i) Atomization of the analyte
ii) Excitation of the analyte
√ iii) Initial ionization of the Ar gas

Q3. Nebulization is the process of sample introduction in ICP source

i) By a process of atomization
ii) By a process of excitation
√ iii) To form a spray mist of the analyte

Q4. Dark current in spectrometers are

√ i) A constant response of signal in absence of radiation
ii) A current not detected by the detectors
iii) Neither of the above

Q5. Spectrometric measurements involves

i) Atomization of the sample
ii) Excitation of the sample
√ iii) Atomization and subsequent excitation