NUCLEAR ENGINEERING

LABORATORY (NE-591)
Chemical Monitoring Lab Practicals
By
FARZANA MAHMOOD, DCS

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INTRODUCTION
• UV/Vis spectroscopy is routinely used in analytical
chemistry for the qualitative and
quantitative determination of different analytes
(Chemical specie under observation in the matrix),
such as transition metal ions, impurities such as
chlorides, sulfides, additives such as nitrite,
hydrazine, etc.
• Spectroscopic analysis is commonly carried out in
solutions

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 Phenomenon Related with Energy :
Absorption & Emission
• If an atom or molecule absorbs a photon its own energy is enhanced and
on the contrary by emitting a photon an atom or molecule becomes less
energetic.
• Molecule can absorb radiation through 3 basic processes, all involve
raising the molecule to higher internal energy level.
• Three basic transitions are Rotational, Vibrational, and Electronic levels.

Electronic level > Vibrational level > Rotational level

occur at (UV/Vis region) (IR region) (microwave or far IR)

• The energy difference between the electronic energy levels is given by the
equation:
E = h
• Any change in the electronic energy is accompanied by a
corresponding change in the vibrational and rotational energy levels
thus result in broadening of absorption band.
• A variety of energy absorptions is possible depending upon the nature of
the bond within the molecule.
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When an atom or molecule absorbs energy, electrons are promoted from
their ground state to an excited state. In a molecule, the atoms can rotate
and vibrate with respect to each other. These vibrations and rotations also
have discrete energy levels, which can be considered as being packed on top
of each electronic level.
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Molecular Transitions
• Molecules containing π-electrons or non-bonding
electrons (n-electrons) can absorb the energy in the
form of ultraviolet or visible light to excite these
electrons to higher anti-bonding molecular orbitals.
• The more easily excited the electrons the longer
the wavelength of light it can absorb. There are
four possible types of transitions (π-π*, n-π*, σ-σ*,
and n-σ*), and they can be ordered as follows:
    n        n  

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Fig: Energy required for electronic transition of  ,  and n
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 VISIBLE AND NEAR-ULTRA VIOLET
MOLECULAR SPECTROSCOPY
• Far/vaccum Ultraviolet region= 100-200 nm
• Near Ultraviolet region= 200-360 nm
• Visible region = 360-800 nm
• Absorption of radiant energy in this wavelength
range results in electronic transitions of electrons
from ground state to excited energy states.
• The absorption of light by a substance can be
used to identify and quantitate that substance,
especially when it is in a homogeneous solution.
• The general shape of the absorption spectrum can
serve to identify the species, whereas the amount
of absorbed light can be used to identify its
concentration.
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Incident light of Transmitted light of
intensity I intensity I
Solution of thickness b
and concentration c

Fig : Test sample is in the form of solution wherein the

solute is absorbing one.

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 Some Terminologies
• Transmittance, 'T': It is the ratio of transmitted
and incident light intensities I and Io respectively.
T = I / Io & % T = 100(I / Io )
• Absorbance, 'A': It is also known as optical
density and extinction. It is logarithm (to the base
10) of the inverse of transmittance, T.
i.e., A = log10 1/T or A = log10 Io/I
• Path length, 'b': It is the internal thickness
(diameter) of the cell in which the test sample is
taken.

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 FUNDAMENTAL LAWS OF ABSORPTION
• BEER'S LAW: It relates the fraction of incident light absorbed through a
sample to the concentration 'c' of the light-absorbing substance, i.e. 'c' is a
reciprocal exponential function of transmittence and a linear function
of absorbance, as
A = kc =  log T =  log I/Io
• Where 'A' is the resulting absorbance, and 'k' is constant for chemical
system.

• LAMBERT'S LAW: The relationship between the relative intensity of the

radiant light emerging from a solution and the depth of the solution was
independently discovered by Lambert. He found that the intensity of the
transmitted energy decreases exponentially or absorbance increases as
the depth 'b' (pathlength) increases. This can be expressed as
A = k'b =  log T =  log I/Io
• Where 'k' ' is constant for chemical system, and 'I' and ' Io' are the
respective intensities of the transmitted and incident beams.

• Both the laws are implemented in a combined form called "Beer-Lambert

Law"

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 "Beer-Lambert Law"
A = abc or A = bc
• a = absorptivity = A/bc
It is a fundamental physical constant for a specific
chemical species at a specific wavelength, and
unlike 'b' and 'c', it cannot be varied by the
operator.
It has units of liters / (gram centimeter)
•  = molar absorptivity = a x molecular or atomic
weight
It has units of liters / (mole centimeter)
• b = path-length in centimeters
• c = concentration expressed in grams/litre or in
molarity (moles/litre)

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 0.1

0.09

0.08

0.07
Absorbance

0.06

0.05

0.04

0.03

0.02

0.01

0
0.1 0.5 1 1.5 2

Concentration

FIG: CALIBRATION CURVE

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LIMITATIONS OF BEER-LAMBERT LAW
• It applies only when the light beam used in
measurement is sufficiently monochromatic.
• Law applies for a limited range of
concentration (dilute) and pathlength.
• If the degree of dissociation, ionization,
hydration and complex formation of the
absorbing solute alters on diluting or
concentrating the solution, apparent
deviations from beer's law are frequently
observed.

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Basic construction of a spectrophotometer

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Diagram of spectrometer placed in CML of KINPOE
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INSTRUMENT COMPONENTS
• The Source: Two sources are used in UV/Vis
spectrometers, which between them can cover the
whole range from 200 nm to 800 nm:
--Tungsten filament lamps  above 360 nm.
--Tungsten-Halogen source in quartz envelope 
above 320 nm.
--Deuterium arc source  below 320 nm
• The Monochromator: Its function is to select a
narrow band of wavelength. It consists of a prism or
a diffraction grating.
• See diagram in the next slide

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• The Sample cell or Cuvette: Cells are made of quartz
or fused silica for the UV/Vis, and glass or plastic for
the visible and are available in matched pairs so that
one of these can be used as reference cell. The optical
windows are highly polished, flat and parallel and the
light path between the inner surfaces of the windows
are closely defined.

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• Detector: It consists of photo-cathode or photo-
multiplier tube.

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 EXPERIMENTS TO BE PERFORMED IN
Chemical Monitoring Laboratory (CML)
• CHEM 1: To study the corrosion behaviour of
Mild steel / Carbon steel in moderately
alkaline to acidic simulated cooling water
containing molybdate and/or nitrite as
inhibitor.
• CHEM 2: Qualitative / Quantitative
determination of anion (Nitrite, Hydrazine,
Chloride) in unknown sample by UV/Vis
spectrophotometer.

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 Objective of Experiments
• The objective is to develop a comprehensive
knowledge regarding the corrosion studies of
secondary cooling water systems. Cooling
water system corrosion causes immediate and
delayed problems. A single failure may force
an unscheduled outage, redirect worker
efforts, contaminate product, compromise
safety, increase equipment expense, violate
pollution regulations, and decrease
productivity.
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 HOT CONDITIONING
• In order to protect PHT system from corrosion HOT
CONDITIONING is performed in NPP.
• Primary Heat Transport System (PHT) at KANUPP is
mainly made of CARBON STEEL (CS)
• In order to protect the internal surfaces of the piping
from corrosion a protective layer of MAGNETITE
(Fe3O4)
(Red Oxide) pH 9.8 – 10.8 (Black Oxide/Magnetite)
FeO + Fe2O3 ───────────→ Fe3O4
Temp = 400°F (205°C)
Pressure = 1500 Psig (48 or 96 hours)

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• Process of protective film growth is slow in the beginning but
it increases as the process progresses.
• In the beginning oxidizing conditions are present and the color
of CRUD is usually yellowy, orange/brownish yellow
(Hematite) but later on as oxidizing conditions are minimized
the color of the CRUD finally converted from grey to DARK
BLACK thus confirming the formation of magnetite layer.
• It is recommended that PHT system must be hot conditioned
as stated above before start-up of plant when:
– Plant is shutdown for more than six months.
– PHT is depressurized and cooled for maintenance or any
other reason.
– Ingress of oxygen has taken place in the PHT system by
any reason.
• [REFERENCE: KNPP.TECHMAN2.1 dated 8 DEC 2009]
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REFERENCES
1. UV/Vis spectroscopy Analytical Chemistry Open Learning
(ACOL) series.
2. Introduction to chemical analysis by Robert Brown.
3. Corrosion and engineering by Fontana Greens.
4. Corrosion for science and Engineering by K R Trethewey.
5. A text book of spectroscopy by O D Tyagi, M Yadav.
6. Chemical Analysis by A K Srivastava, P C Jain.
7. Principles of Quantitative chemical analysis by Robert de
Levie.
8. Herro H. M., Port R. D. 1993 The NALCO Guide to Cooling
Water Systems Failure Analysis NALCO Chemical
Company .
9. Mustafa C. M.,et.al. 1997 British corrosion journal, vol 32,
no.2, pg 133.

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