Dedication

From the bottom of my heart and with all my respect, I dedicate this work to my little
BOUDEKEN’s family. To my parents RACHID and B.HAKIMA, my lovely sisters
HANANE and AMINA and their four kids, to A.DJOUABI and every teacher, everyone was
the reason I learned.

I want to say thank you to my parents, I am who I am today because of you, you were always
with me, so whatever I do is nothing in front of your worth. Hope you are proud of me.

At the end, with all my love and my respect I want to say thank you to my special DJOUABI
AYOUB for being always with me.

Thanks
Firstly, I would like to thank ALLAH and say Alhamdulillah for the help, courage and

patience that Allah has given me to accomplish this work.

I wanted to introduce my co-supervisor Dr. B.GUEDIOURA for his help and advice.

I express my deep thanks to my supervisor Dr. N.NASRALLAH for his critical eye to

improve the quality of my work.

All my gratitude goes to madam BECHOHRA for chairing my end of study project and

madam KERCHICHE who did us the honor to examine this end of study project.

Finally, I would like to say thank you for everyone was someday the reason of

understanding and learning.

 Summary

General introduction...................................................................................................................02

Part Ⅰ: Bibliographic study

Chapter Ⅰ: general information on the aim materials

Ⅰ.1 Bentonite.................................................................................................................................04

Ⅰ.1.1 Definition.............................................................................................................................04

Ⅰ.2 Cobalt......................................................................................................................................05

Ⅰ.2.1 Definition.............................................................................................................................05

Ⅰ.2.2 Cobalt isotopes....................................................................................................................05

Ⅰ.2.3 Cobalt toxicity.....................................................................................................................05

Chapter Ⅱ: general information on the radioactivity

Ⅱ.1 Basic concept of radioactivity.............................................................................................06

Ⅱ.1.1 History................................................................................................................................06

Ⅱ.1.2 Definition...........................................................................................................................06

Ⅱ.1.3 definition of the atom........................................................................................................06

Ⅱ.1.4 Rays emission....................................................................................................................06

Ⅱ.1.5 Effect of radioactivity on humans and environment.....................................................08

Ⅱ.2 radioactivity waste...............................................................................................................08

Ⅱ.2.1 Definition...........................................................................................................................08

Ⅱ.2.2 radioactive waste classification........................................................................................08

Ⅱ.3 radiation-matter interaction...............................................................................................09

Chapter Ⅲ: Gamma spectrometry

Ⅲ.1 introduction.........................................................................................................................10

Ⅲ.2 Definition.............................................................................................................................10

Ⅲ.3 interaction of gamma radiation with matter...................................................................10

I
Ⅲ.4 Operation of the gamma spectrometry system................................................................11

Ⅲ.5 Gamma spectrometry efficiency.......................................................................................12

Chapter Ⅳ: Adsorption

Ⅳ.1 Introduction........................................................................................................................13

Ⅳ.2 Definition.............................................................................................................................13

Ⅳ.3 Types of adsorption............................................................................................................14

Ⅳ.4 Comparison between the two types of adsorption...........................................................14

Ⅳ.5 Adsorption characteristics.................................................................................................15

Ⅳ.6 Adsorption kinetic..............................................................................................................15

Ⅳ.6.1 Pseudo first order model.................................................................................................16

Ⅳ.6.2 Pseudo second order model............................................................................................16

Ⅳ.6.3 Intra-particle diffusion....................................................................................................16

Ⅳ.7 Thermodynamic adsorption..............................................................................................17

Ⅳ.8 Modeling of adsorption isotherms.....................................................................................17

Ⅳ.8.1 Langmuir’s model............................................................................................................17

Ⅳ.8.2 Freundlich’s model..........................................................................................................18

Part Ⅱ: Experimental part

Chapter Ⅴ: Materials and methods

Ⅴ.1 NuR reactor .........................................................................................................................20

Ⅴ.2 Gamma spectrometry..........................................................................................................20

Ⅴ.3 Materials...............................................................................................................................21

Ⅴ.3.1 Solution and products used..............................................................................................21

Ⅴ.3.2 Small materials..................................................................................................................22

Ⅴ.3.3 Apparatus...........................................................................................................................22

Ⅴ.4 Experimental protocols........................................................................................................23

II
Ⅴ.4.1 Protocol for doping the water in the primary circuit of the NuR reactor...................23

Ⅴ.4.2 Preparation of initial concentration................................................................................24

Ⅴ.4.3 Preparation of samples.....................................................................................................24

Chapter Ⅵ: Results and discussion

Cobalt adsorption study on raw bentonite

Ⅵ.1 Introduction........................................................................................................................25

Ⅵ.2 Calibration of the gamma spectrometry chain................................................................25

Ⅵ.2.1 Energy calibration...........................................................................................................25

Ⅵ.2.2 Efficiency calibration......................................................................................................27

Ⅵ.2.3 Calibration in activity.....................................................................................................29

Ⅵ.2.4 Background noise............................................................................................................30

Ⅵ.3 Analysis of experimental results........................................................................................31

Ⅵ.3.1 Effect of initial concentration.........................................................................................31

Ⅵ.3.2 Modeling of adsorption equilibrium isotherms............................................................31

Ⅵ.4 Effect of contact time on adsorption equilibrium............................................................35

Ⅵ.5 Kinetic modeling of cobalt adsorption on raw bentonite................................................36

Ⅵ.5.1 Pseudo first order............................................................................................................37

Ⅵ.5.2 Pseudo second order .......................................................................................................38

Ⅵ.5.3 Intra-particle diffusion....................................................................................................40

Ⅵ.6 Study of the thermodynamic parameters.........................................................................41

Conclusion ...................................................................................................................................43

III
 Tables list

Table Ⅰ.1: Characteristics of cobalt 60

Table Ⅳ.1: Different criteria for physisorption and chemisorption

Table Ⅳ.2: References of the separation factor

Table Ⅵ.1: N° channel / energy

Table Ⅵ.2: Detector efficiency measurements

Table Ⅵ.3: Langmuir separation factor according the initial concentration

Table Ⅵ.4: Langmuir and Freundlich parameters of equilibrium adsorption isotherms of

cobalt on raw bentonite at temperature 313 K

Table Ⅵ.5: Resume of the pseudo first and second order equations

Table Ⅵ.6: Pseudo first / second order results of the adsorption of cobalt 60 on raw bentonite
at C = 100 mg/l

Table Ⅵ.7: Parameters of the intra-particle diffusion

Table Ⅵ.8: The thermodynamic parameters of adsorption of cobalt 60 on raw bentonite

IV
 Figures list

Figure Ⅰ.1: Bentonite clay powder

Figure Ⅱ.1: Decay of an unstable nucleous

Figure Ⅲ.1: Different geometry types of germanium hyper pure detector

Figure Ⅲ.2: Block diagram of gamma spectrometry system

Figure Ⅳ.1: Diagram represents the adsorption technique

Figure Ⅳ.2: Diagram represents the two types of adsorption

Figure Ⅴ.1: Controm room of NuR reactor

Figure Ⅴ.2: Cross section of NuR reactor

Figure Ⅴ.3: Detector system and detection room

Figure Ⅴ.4: Raw bentonite

Figure Ⅴ.5: Filter paper

Figure Ⅴ.6: Micro-syringe

Figure Ⅴ.7: Detector Ge (HP)

Figure Ⅴ.8: Precision balance

Figure Ⅴ.9: Doped primary circuit water

Figure Ⅴ.10: Experimental protocol for the adsorption of cobalt 60 on raw bentonite

Figure Ⅵ.1: Graph of intensity as a function of channel number of standard sources

Figure Ⅵ.2: Energy calibration line of the gamma spectrometry chain

Figure Ⅵ.3: Detector efficiency calibration graph

Figure Ⅵ.4: Gamma spectrum of the standard source of cobalt

Figure Ⅵ.5: Gamma spectrum of the detector’s background noise

Figure Ⅵ.6: Initial concentration effect of adsorption of cobalt 60 ions

V
Figure Ⅵ.7: Nonlinear Langmuir isotherm

Figure Ⅵ.8: Langmuir isotherm linearized at T = 313 K

Figure Ⅵ.9: Nonlinear Freundlich isotherm

Figure Ⅵ.10: Freundlich isotherm linearized at T = 313 K

Figure Ⅵ.11: Effect of contact time on adsorption of cobalt 60 on raw bentonite

Figure Ⅵ.12: Plots of pseudo first order kinetics at C = 100 mg/l and pH = 5.5

Figure Ⅵ.13: Plots of pseudo second order kinetics at C = 100 mg/l and pH = 5.5

Figure Ⅵ.14: Plots of the kinetics model of intra-particle diffusion for the temperatures
studies at C = 100 mg/l and pH = 5.5

Figure Ⅵ.15: Plot of variation ln(kd) as a function of (1/T)

VI
 General introduction

Nowadays, due to the industrial development the environmental contamination increases so

the society must solves the problem by relying on various sciences, one of these sciences is
chemical engineering. It is mastering and solving environmental problems by several different
methods.

Chemical engineering refers to the application of physical chemistry on an industrial scale,

with the aim of transforming matter, it is interested in the mechanism of reactions.

The industrialization of the chemical reaction consists in implementing it under the most
economical conditions possible and while working. It is up the chemical engineering to define
the facilities where chemical reactions take place and their operating conditions.

Chemical engineering encompasses many fields, including the nuclear field, which is known
for its waste hazard.

In particular, radioactive waste containing a variety of radionuclides can severely pollute the
environment if the pollutants are not well treated. The source of this radioactive waste is
usually from interactions that take place at level of NuR reactor (Nuclear Research) despite
the optimization of the materials and the chemical composition of the water in the primary
circuit, so we notice a formation of colloidal particles which circulate in the primary circuit
and are deposited on the walls of the reactor.

Among the most used processes in these cases is adsorption because it is a very efficient
pollutant removal technique, it is based on the nature of the pollutant (adsorbate) and the
adsorbent used.

In our work, we will study the elimination of corrosion product which is Cobalt 60 (has a long
half-life of toxicity) by raw Maghnia Bentonite due to its specific physical and chemical
properties, is regarded as one of the most promising candidates for buffer/backfill material
used in disposing high level nuclear waste in deep.

The aim of this work is based on the understanding of the gamma spectrometry technique and
its applications to the recognition and origin of ultra-trace ionic elements in the fluid of the
NuR reactor.

Also, study the characterization of raw bentonite, identify the influence of contact time and
temperature at 298, 313, 333, 353 K on the adsorption of 60Co on raw bentonite and its
adsorption capacity, measure the 60Co adsorption isotherms and correlate the experimental
data with different adsorption models, and conduct a comprehensive analysis of the process
studying.

2
 General introduction

This study has three parts: bibliographic study, materials and methods, results and discussion.

The bibliographic study is based on the understanding of radioactivity, gamma spectrometry

and the adsorption technique.

In the second part, we describe the experimental protocol for sample preparation and
adsorption experiments.

The third part is devoted to the interpretation of the experimental results.

At the end, a general conclusion allowing a synthesis of this work.

3
 Part Ⅰ
Bibliographic study
 Chapter Ⅰ
General information
on the aim material
 Chapter Ⅰ: General information on the aim materials

Ⅰ.1. Bentonite

Ⅰ.1.1. Definition

Due to its specific physical and chemical properties is considered as one of the most
promising candidates for insulting material for the disposal of high level nuclear waste.

Therefore, many laboratory studies on Bentonite samples from various deposits worldwide
have been conducted to evaluate the suitability of this material as an insulating and its
sorption behavior.

Raw Bentonite is colloidal clay, it is of volcanic and hydrothermal origin. It has very good
water retention capacity.

Due to the hydrothermal transformation of ash from glass-rich volcanic tuffs results in the
formation of clay minerals, which is a part of the smectite group.

The clay rocks thus formed are called bentonite, after the deposit located near Fort Benton
(Wyoming, United States). Being essentially made up of montmorillonite (rich in silica),
which explains its water retention capacity because montmorillonite is a particularly swelling
type of smectite. [1 – 3]

In Algeria, the most economically important bentonite deposits are found in the western
Algeria.We note in particular the careers of Maghnia (Hammam Boughrara) and Mostaganem
(M’zila). [2 – 6]

Figure Ⅰ.1: Bentonite clay powder.

4
 Chapter Ⅰ: General information on the aim materials

Ⅰ.2. Cobalt

Ⅰ.2.1. Definition

Cobalt is a stable chemical element, with symbol Co, atomic number of 27 and mass number
of 59.it is silver gray metal, it founds in the earth’s crust in chemical combined form. The
main ores of cobalt are Limit (Cobalt Sulphides) and Cobaltin (Cobalt Arseniosulfide). [7]

59
Co can also be produced artificially by nuclear reaction of iron 58Fe to 59Fe* then this latter
use the γ and β decays to gives 59Co

Fe58 +n → Fe ¿59 I.1

Ⅰ.2.2. Cobalt isotopes

There are several cobalt isotopes, like 48Co, 51Co, 57Co…

But only 57Co, 58Co, 60Co are the most isotopes treated because we found it like corrosion
products in the nuclear reactors due to their long period, especially 60Co

60
Co is a neutron activation product formed from the structural materials of nuclear reactors.
Is one the most isotope treated due to its longest half-life.

Radio-cobalt represents 47% of total gamma activity.

Table Ⅰ.1: Characteristics of Cobalt 60. [8]

Radioactive Period (half-life) 5.27 years

Mass Activity 4.2 1013 Bq.g-1
β- decay
Main Emission Emax = 318 KeV (100%)
γ emission
(emission yield per 100 decays) E = 1332 KeV (100%)
E = 1173 KeV (100%)

Ⅰ.2.3. Cobalt toxicity

57 58 60
Stable cobalt has toxicity at high concentrations, especially its isotopes Co, Co, Co
because are radioactive.

The high concentrations of the cobalt can cause poisoning like kidneys, nervous system, and
pulmonary fibrosis.

5
 Chapter Ⅱ
General information
on the radioactivity
 Chapter Ⅱ: General information on the radioactivity

Ⅱ.1. Basic concept of radioactivity

Ⅱ.1.1. History

The discovery began in the nineties of the nineteenth century with the discovery of unknown
radiation called X-rays.

Antoine henry Becquerel in 1896 conducted a series of experiments to find out the ability of
uranium. He used to place different bodies on a photographic sheet wrapped in a black
protection sheet and sprayed uranium on another black sheet above it, so that he would get
those objects placed between uranium and the photographic sheet. Then he would purify the
newspaper from time to time and it would appear each time a theoretical photographic scheme
of the body, through these experiments proved the source of radiation, which is uranium.

Marie Curie and her husband completed those experiments, and they worked to separate any
elements that were responsible for radioactivity in uranium for two years, until she was able
to isolate two new elements of uranium ore, called Polonium and Radium.

Curie found that radium is more active than uranium, and that energy and radioactivity that
penetrated the substance was an atomic, not a chemical, source.

The physicist Ernest Rutherford paid attention to the atomic nature of radioactivity, and found
that radioactive material undergoes natural abatement and emits radiation that represents
unstable and highly charged energy molecules capable of penetrating matter, which are alpha,
beta particles and the electromagnetic beam gamma.

Ⅱ.1.2. Definition

Divided into two Latin words which is radius (rays), activus (activity).

Radioactivity is a random transformation of an unstable nucleus into a more stable nucleus,

with emission of alpha, beta particles and the electromagnetic beam gamma.

Ⅱ.1.3. Definition of the atom

It is the smallest particle of an element which builds the element properties.

Each atom has nucleus contains neutrons and protons, revolving around nucleus a negative
charge particles called electrons.

Ⅱ.1.4. Rays emission

The nucleus is made of neutrons and protons, and is the center of the atom. If it gives
radiation that is unstable, means that gives parts of its interior in the form of energy or

6
 Chapter Ⅱ: General information on the radioactivity

molecules, this atom is called an active atom, and the real sects are called a radioactive
isotope.

Figure Ⅱ.1: Decay of an unstable nucleus.

 Alpha decay

An atom with a nucleus that is heavy in charge of protons and neutrons, spits out two neutrons
and 2 protons in order to slim down and become more stable. This is call alpha particles,
which has masse of 4 and charge of 2, it is basically or the same as Helium atom 42He

A
Z X → A−4
Z−2Y + α II.1

 Beta decay

There are two types of Beta decay.

When the beta particles has a mass oh zero and charge of (-1), basically the same as electron,
called β−¿¿

When the beta particles has a mass of zero and charge of (+1), called positron particle β +¿¿

In β−¿¿ neutron converted on proton and electron, that is basically what happens. That is why
the atomic number increases.

A
Z X → Z+1AY + β−¿+υ ¿ II.2

In β +¿¿ proton converted on neutron and positron, that is why the atomic number decreases.

7
 Chapter Ⅱ: General information on the radioactivity

A
Z X → Z−1A Y + β +¿+υ¿ II.3

 Gamma decay

Has a mass and charge of zero 00γ

γ ray is an electromagnetic radiation with high energy photons, with accompanies the
emission of α and β radiations.

Ⅱ.1.5. Effect of radioactivity on humans and environment

Used in medicine: medical imaging, oncology

It is used as a way to calculate the age of the Earth

Energy source for discoveries of the universe

Fire alarms contain Americium, which helps in forming a steady electric current

Ⅱ.2. Radioactive waste

Ⅱ.2.1. Definition

It is a by-product produced after being used inside a nuclear reactor contains radioactive
material.

It can be a kind of waste in gas, liquid or solid form.

Ⅱ.2.2. Radioactive waste classification

 High level

Accounts for 95% of the total radioactivity produced in the nuclear reactor. It can have short
or long lived components, this type of nuclear waste is very dangerous.

 Intermediate level

Accounts for 4% of the total radioactivity. This type includes refurbishment waste and ions-
exchange resins.

 Low level

Accounts 1% of the radioactivity of all radioactive waste. This type includes hospitals,
nuclear reactors, laboratories and industries.

8
 Chapter Ⅱ: General information on the radioactivity

Radioactive waste classification according to the specific activity and radioactive period of
the radionuclides.

Specific activity is the number of nuclei that decay per unit time in Becquerel (Bq):

−dN
A= ¿ A=λN II.4
dt

The negative sign means as time increases the number of undecayed nuclei present decreases.

Radioactive period is the half-life of a radioactive substance.

All types of radioactive wastes have their own clean-up procedures.

Ⅱ.3. Radiation-matter interaction

The most important interactions and the most study are:

 Photoelectric effect
 Compton diffusion
 Creation of electron-positron pairs

There are other interactions like: Thomson diffusion, Rayleigh diffusion, in this case the
diffused photon has the same energy as the incident photon but with different direction.

9
 Chapter Ⅲ
Gamma spectrometry
 Chapter Ⅲ: Gamma spectrometry

Ⅲ.1. Introduction

Gamma spectrometry is an electromagnetic radiation emitted as a result of alpha or beta

radiation when it produces a new nucleus in an excited state. The energy released is in the
form of high potential photons that penetrate matter this energy expresses by:

C
E=h .υ=h . III.1
λ

With

h: Plank constant

υ: Wave frequ.3.ency

λ: Wave length

Research on radioactivity has made it possible to provide tools and instruments to better
understand these active phenomena and to improve the field of medicine, biology and
geology. For this we speak of gamma spectrometry.

Ⅲ.2. Definition

Gamma spectrometry is a nuclear measurement technique. Used to identify radioactive

element by measuring the energy of the gamma rays emitted and determine their activity.

Ⅲ.3. Interaction of gamma radiation with matter

Gamma particles are detected through their interactions with matter by giving up part of their
energy to one or more electrons.

The type of interaction depends on the energy of the incident photons and the matter. We
distinguish three types of interaction: [9 – 12]

 Photoelectric effect

Total absorption of gamma photons by an atom whose energy is transformed to an electron

which will be ejected from one of the electron shells of the atom.

 Compton effect

Part of the photon energy is transformed to an electron, usually an electron from the outer
layers.

10
 Chapter Ⅲ: Gamma spectrometry

 Materialization effect

Total absorption of photon energy to create a positron electron pair.

Ⅲ.4. Operation of the gamma spectrometry system

The detection of gamma radiation is based on its interaction with matter. This aims to connect
the electrical signal to energy, then count the different energies obtained.

The photon detector system is composed of an electronic detector, a preamplifier, an

amplifier, an analog/digital converter and multichannel analyzer, computer, which aims to
convert the radiation into an electrical signal with protection of the energy and quantitative
properties of the radiation.

 Detector

Generally of the Germanium crystal semiconductor type, lead structure. Ge(HP) detectors
exist in three forms: planar, coaxial and well.

 Planar detectors: have a cake shape, 3cm thickness, have a carbon entry window. It is
used for low energy photons and thin samples.
 Coaxial detectors: have a cylindrical shape and a hollow central part with beryllium or
aluminum window, it is used for high energy photons and large samples.
 Well detectors: have an aluminum entry window. It is used for very small quantity
samples.

Figure Ⅲ.1: Different geometry types of germanium hyper pure detector.

 Preamplifier

An integrative assembly that will integrate the signal to make the link with the energy.

11
 Chapter Ⅲ: Gamma spectrometry

 Amplifier

Signal shaping, in order to minimize electronic noise to obtain a Gaussian signal.

 Analog/digital converter and multichannel analyzer

The converter transforms the continuous signal aptitude that is output from the amplifier into
a number proportional to the energy deposited in the crystal.

The analyzer collects, classifies and stores information in different channels, each
corresponding to energy.

With this method we obtain a real time histogram in which the energy deposited in the crystal
is linked to the channel number and the number of hits in channel is proportional to the
number of photons.

 Computer

Display signal. [9]

Figure Ⅲ.2: Block diagram of gamma spectrometry system.

Ⅲ.5. Gamma spectrometry efficiency

The quality of a gamma spectrometer depends on its ability to detect photon lines and to
differentiate them from each other.

12
Chapter Ⅳ
Adsorption
 Chapter Ⅳ: Adsorption

Ⅳ.1. Introduction

The adsorption process ranks first in the scientific and practical field. It is one of the most
important technologies nowadays.

It is used for depollution and purification in several field such as nuclear, petroleum,
pharmaceutical… and others.

In this chapter we will understand more about what actually adsorption means.

Ⅳ.2. Definition

Adsorption is a treatment process well suited to eliminate a very wide variety of toxic
compounds in our environment.

It is the collection of matter (liquid or gaseous) in the form of particles, ions or atoms on the
solid surface.

The matter on the solid surface called adsorbate, the solid surface called adsorbent and the
particles that are not located on the adsorbent and are present in the solution called adsorptive
species.

If the substance returned from adsorbent to solution this phenomenon is called desorption.

Of which adsorption is result of the adsorbent energy. During this process there is a transfer
of the material of the aqueous phase to the solid surface. The nature of the bonds formed as
well as the quantity of energy released during the retention of a molecule on the solid surface
allowing two types of adsorption to be distinguished: physical adsorption and chemical
adsorption. [13 – 14]

Figure Ⅳ.1: Diagram represents the adsorption technique.

13
 Chapter Ⅳ: Adsorption

Ⅳ.3. Types of adsorption

 Physical adsorption (physisorption)

When adsorbate molecules or atoms are held to the solid surface by Van Der Waal’s forces.

Van der Waal’s force, exist in all molecules, it is relation created between the less negative
and the more negative (-δ +δ) by the electrode distributes in the last layer of the molecule.

It is a force of attraction between negative end of permanent dipole and the positive of
permanent dipole of another molecule.

Van der Waal’s force characterizes by the contact area as it is big as the force is, the
polarizability and molecular size, it means the more electrons there are the more forces exist.

 Chemical adsorption (chemisorption)

When adsorbate molecules or atoms are held the solid surface by chemical bonds, it can be
ionic bonding or covalent bonding.

Figure Ⅳ.2: Diagram represents the two types of adsorption.

Ⅳ.4. Comparison between the two types of adsorption

Table Ⅳ.1: Different criteria for physisorption and chemisorption. [15]

Properties Physisorption Chemisorption

Bond Van der Waal’s force Chemical bonds
Temperature Low High
Heat of adsorption 1 to 10 Kcal.mol-1 > 10 Kcal.mol-1
Desorption process Easy Difficult
Kinetic Very fast Slow
Layer formation Multilayer Monolayer

14
 Chapter Ⅳ: Adsorption

Reversibility Reversible Irreversible

Ⅳ.5. Adsorption characteristics

 Specificity of adsorbent
 Nature of adsorbate
 Reversibility of the process

Physical adsorption is reversible process due to the weak Van der Waal’s forces of attraction;
on the contrary, chemical adsorption is irreversible due to the chemical bonds that give new
materials.

 Enthalpy of adsorption

Temperature of physical adsorption is low because of the Van der Waal’s force that is a weak
force, ∆Hphy < 20 or 40 kj/mol that is low enthalpy

Temperature of chemical adsorption is high because of the chemical bonds, ∆Hch between 80
to 240 kj/mol that is high enthalpy.

Therefore physisorption is weak and chemisorption is strong.

 Activation energy

The minimum energy required to convert reaction into products.

It is very less in physisorption and high activation in chemisorption.

 Layers of adsorption

Physisorption: multi-molecular layers are formed under high pressure

Chemisorption: uni-molecular

 Surface area of adsorbate

Ⅳ.6. Adsorption kinetic

The adsorption kinetic is the solute retention rate as a function of contact time. It expresses
the adsorption efficiency.

It means the speed with which thermodynamic equilibrium is reached as a function of the
adsorbate diffusion rate and the interaction adsorbate-adsorbent

15
 Chapter Ⅳ: Adsorption

There are two kinetic adsorption models, the first and the second pseudo order.

Ⅳ.6.1. Pseudo-first order model

This kinetic model is known by the Lagergren equation which assumes that the retention rate
of a solute over time is proportional to the difference between the amount adsorbed at
equilibrium and that adsorbed at a time t

d qt
=K 1 ( q e −q t ) IV.1
dt

By integration, becomes:

K1
log ( q e −q t )=log qe − ( )
2.3
t IV.2

With

qe: amount of adsorbate at equilibrium per gram of adsorbent (mg.g-1)

t: time of contact (min)

k1: adsorption rate constant for the first order (min-1)

Ⅳ.6.2. Pseudo second order model

Model of Ho and McKay

d qt 2
=K 2(qe −q t ) IV.3
dt

By integration, becomes:

t 1 t
= + IV.4
qt K 2 . qe 2 q e

With

K2: adsorption rate constant for the second order (g.mol-1.min-1). [16 – 20]

Ⅳ.6.3. Intraparticle diffusion

An intraparticle diffusion rate parameter has been defined characteristic of the rate of
diffusion after the early stages of the adsorption.

16
 Chapter Ⅳ: Adsorption

The adsorption rate is controlled by the slowest step of the process so knowing the limiting
step of the adsorption process is an important factor, according to Webber and Morris, the
kinetic expression of intraparticle diffusion is given by the equation below and which allows
determining the type of diffusion mechanism:

q t=K id × t 0.5 +C IV.5

Kid : the intraparticle diffusion rate constant

C: constant expresses the thickness of the boundary layer

Ⅳ.7. Thermodynamic adsorption

The thermal adsorption study can be exothermic or endothermic, for this the most important
measurement is the heat of adsorption released (enthalpy) which makes it possible to
differentiate physisorption and chemisorption.

Ⅳ.8. Modeling of adsorption isotherms

This study aims know the maximum capacity possessed by adsorbents.

Among the most popular models are those of Langmuir and Freundlich.

Ⅳ.8.1. Langmuir’s model

The Langmuir equation is valid for a monolayer adsorption on a surface with an identical
finite number of sites, it is expressed by:

qmax . K L .C e
q e= IV.6
(1+ K L .C e )

With

qe: adsorption capacity at equilibrium (mg.g-1)

qmax: maximum adsorption capacity (mg.g-1), in order to form a complete monolayer on the
surface

Ce: concentration of the adsorbate at equilibrium (mg.l-1)

KL: the Langmuir adsorption equilibrium constant (l.mg-1)

KL linked to the affinity of the surface sites for the adsorbates and to the adsorption energy. It
is equal to the ration of the rate constants of adsorption and desorption.

17
 Chapter Ⅳ: Adsorption

In the case of a large quantity of adsorbed solute, the term (K L . Ce) is greater than 1 (>1),
means that qe tends towards qm

So by the linearization of (Ⅳ.6):

1 1 1 1
= (
qe K L . qmax )( ) ( )
Ce
+
qmax
IV.7

But, in the case of a small quantity of adsorbed solute, the term (K L . Ce) is less than 1 (<1)
and it is neglected. So the Langmuir equation is reduced to a direct relation between
adsorption capacity and the equilibrium concentration of liquid phase adsorbate

q e ¿ q max . K L . Ce IV.8

The essential characteristics of the Langmuir isotherm can be expressed by an adimensional

constant called separation factor or equilibrium parameter RL defined by:

1
R L= IV.9
(1+ K L . C 0)

C0: initial concentration of the adsorbate in the solution

This table below gives the meaning of the separation factor RL

Table Ⅳ.2: References of the separation factor.

RL Value Type of isotherm

RL > 1 Unfavorable

RL = 1 Linear

0 < RL <1 Favorable

RL = 0 Irreversible

 Assumption of Langmuir adsorption isotherm:

Only one monolayer forms.

All sites on the surface are equivalent.

No adsorbate-adsorbate interactions.

Ⅳ.8.2. Freundlich’s model

18
 Chapter Ⅳ: Adsorption

Freundlich's equation is an empirical model based on adsorption on heterogeneous surfaces. It

is used in the case of the possible formation of more than one adsorption monolayer on the
surface and the sites are heterogeneous with different fixing energies. The isotherm is
expressed by the equation:

q e =K F .C 1/e n IV.10

With the linear form:

ln (q¿¿ e )=ln ( K ¿¿ F )+ ( 1/n ) . ln(C¿¿ e )¿ ¿ ¿ IV.11

KF: Freundlich adsorption constant

n: Constant depending on the nature of the adsorbate and the temperature, it express the
intensity of adsorption.

 Assumption of Freundlich model:

Heterogeneous surface.

No mobility of molecules on the surface and no interaction.

19
 Part Ⅱ
Experimental part
 Chapter Ⅴ
Materials and
methods
 Chapter Ⅴ: Materials and methods

Ⅴ.1. NuR reactor (Nuclear Research)

All the neutron experiments are carried out in a nuclear reactor called the NuR reactor. It is a
classic open heart with swimming pool type.

The core is made up of 17 plate fuel assemblies enriched with 20% of Uranium 235 which
constitutes the fissile material. It is cooled and moderated with demineralized light water with
a power equal to 1 MW thermal and a neutron flux reaching a magnitude of 1013 n.cm3.s-1

There are 12 standard assemblies with 19 plates and 5 control assemblies with 14 plates, in
order to leave space for the location of the control bars.

The core is surrounded by a graphite reflector placed in the grid around the fuel elements, the
whole submerged in a volume of water of approximately 64 m 3 in a stainless steel swimming
pool 3 m in diameter and 9 m in height, itself surrounded by a concrete wall.

Figure Ⅴ.1: Figure Ⅴ.2:

Control room of NuR reactor Cross section of NuR reactor.

Ⅴ.2. Gamma spectrometry

The CANBBERA brand gamma spectrometry chain is characterized by:

 The detection room is a lead castle 114 mm thick with sheets of 3 mm of tin and 5 mm
of copper, the purpose of which is to obtain noise level.
 Semiconductor detector of p-type GX-3519, connected to a DSA system (digital
spectrum analyzer).
 Preamplifier and an analyzer with 4096 ORTEC channels incorporating an amplifier.
 Appropriate gamma-vision software developed by ORTEC.

20
 Chapter Ⅴ: Materials and methods

Figure Ⅴ.3: Detector system and detection room.

Ⅴ.3. Materials

Ⅴ.3.1. Solution and products used

 Nitric acid (HNO3) , concentrated at 60 % of 1.38 density (Cheminova)

 Demineralized water produced at the reactor with an electrical conductivity lower than
0.75 μs
 Acetone (C3 H6 O)
 26 liters of water from the primary circuit of the reactor (extracted after
homogenization)
 Cobalt 59
 Cobalt 60
 Raw bentonite (from Maghnia)

Figure Ⅴ.4: Raw bentonite.

21
 Chapter Ⅴ: Materials and methods

Ⅴ.3.2. Small materials

 Filter paper
 Aluminum paper
 Laboratory glassware: beakers, pipettes, flasks, Erlenmeyer, funnels, test tubes
 Micro-syringe
 Magnetic bars
 Wash bottle
 Clamp
 Gloves
 Mask

Figure Ⅴ.5: Filter paper.

Figure Ⅴ.6: Micro-syringe.

Ⅴ.3.3. Apparatus

 Hyper Pure Germanium detector

 Precision balance SARTORIUS’s brand, precision 0.1 mg
 Magnetic stirrer with hot plate, VELP’s brand
 PH meter
 Oven, BINDER’s brand
 Centrifuge, ROLEO’s brand model 2036
 Dosimeter films

22
 Chapter Ⅴ: Materials and methods

Figure Ⅴ.7: Detector Ge (HP). Figure Ⅴ.8: Precision balance.

Ⅴ.4. Experimental protocols

Ⅴ.4.1. Protocol for doping the water in the primary circuit of the NuR
reactor

Before the adsorption experiment, we took 10 liters of water from the primary circuit at the
sampling point of the latter after homogenization of the water. The primary water sample was
taken after treatment with ion exchange resins (Amberlite) because safety standards prohibit
any sampling action in the active zone (near the reactor core).

The analysis of the gamma spectrum shows that the ions resulting from the corrosion products
are in ultra-traces (<0.01 ppm) for this reason we have doped the 10 L of primary water
extracted, with 10 g of natural Cobalt ( 59Co) and 1, 25 mg of radioactive cobalt ( 60Co) by
adding 1 mL of concentrated nitric acid.

Figure Ⅴ.9: Doped primary circuit water.

23
 Chapter Ⅴ: Materials and methods

Ⅴ.4.2. Preparation of initial concentrations

The solution of the primary circuit water obtained after doping and dilution is initially
concentrated to C0 = 1000 mg / l (initial concentration). This solution was diluted into nine
daughter concentrations C1 = 20 mg / l, and C2 = 40 mg / l, C3 = 80 mg / l, C4 = 100 mg / l, C5
= 250 mg / l, C6 = 500 mg / l. For the preparation of concentration C1, in a beaker, we take
V0 = 2 ml of stock solution, dilute it with demineralized water in a volumetric flask to a
volume V1 = 100 mL. The volume V 0 taken from the stock solution for the dilution was
calculated by the relationship:

C 0 V 0 =C1 V 1 V.1

Ⅴ.4.3. Preparation of samples

In a beaker, 25 ml of primary circuit water doped with Co are mixed with 125 mg of raw
bentonite. The mixture obtained is stirred (450 rev / min) for an interval of time ∆t. at the end
of the agitation, the adsorbent is recovered by filtration and then analyzed by gamma
spectrometry for an acquisition time of 1200 s. The obtained spectrum will be the objective of
analysis. This protocol is repeated for several increasing time intervals (from 5 min to 90 min)
by varying the initial concentration at room temperature, and for the four isotherms (298, 313,
333, 353) K at the concentration 100 mg / l.

Figure Ⅴ.10: Experimental protocol for the adsorption of cobalt 60 on raw bentonite.

24
 Chapter Ⅵ
Results and discussion
Cobalt adsorption
study on raw
bentonite
 Chapter Ⅵ: Results and discussion

Ⅵ.1. Introduction

In this chapter we will present the analysis results of our samples obtained by the γ
spectrometry technique. This measurement technique is used to quantify a large number of
radionuclides via the energy of gamma radiation emitted. It is based on the detection of the
interaction between radiation and matter by a hyper-pure germanium Ge (HP) detector.

We will also present the results obtained from kinetic and thermodynamic modeling of
adsorption of radioactive corrosion products produced by neutron irradiation in the water of
the primary circuit of the NuR reactor. We will study of 60Co on raw Maghnia bentonite as an
adsorbent, which was used for the purification of the water in the primary circuit of the NuR
reactor.

Ⅵ.2. Calibration of the γ spectrometry chain

This step is very important in order to be able to work, because the acquisition of gamma
spectra is given according to the channel numbers while the identification of the radioelement
(cobalt 60 in our case) is done by means of the energies of the peaks. So the efficiency of the
detector is an important parameter.

Ⅵ.2.1. Energy calibration

The energy calibration is therefore necessary to identify the radioactive elements, establishing
a linear relationship between the channel number and the energy deposited in the crystal.

For this we used 3 standard sources which are respectively 60Co, 152
Eu and 137
Cs. The peaks
are selected and their corresponding energy value is assigned to them. We thus obtain the
spectrum of a set of energy-distributed peaks added to a background noise. The peaks
obtained represent the energy of the incident photons and make it possible to identify the
radioelement that emits gamma radiation.

We obtain a spectrum with the channel number on the x-axis and the number of strokes (the
intensity) in the corresponding channel using standards. The energy spectrum of standard
sources is given in the figure (Ⅵ.1) and table (Ⅵ.1)

25
 Chapter Ⅵ: Results and discussion

7.50E4

Gamma spectrum of standard sources

6.00E4 60
Co
Number of stokes (u,a)

152
Eu
137
Cs
4.50E4

3.00E4

1.50E4

0.00
500 1000 1500
N° Channel

Figure Ⅵ.1: Graph of intensity as a function of channel number of standard sources.

Table Ⅵ.1: N° channel/energy.

N° Channel Energy
329.05 121.87
660.31 244.46
928.75 344.16
1197.58 443.81
1784.59 661.40
2100.95 778.66
2339.75 867.18
2600.54 963.85
2929.15 1085.66
3000.01 1111.92
3164.97 1173.07
3505.07 1299.14
3594.98 1332.46
3798.97 1408.08
4127.54 1529.87

26
 Chapter Ⅵ: Results and discussion

From these results we draw the corresponding graph (figure (Ⅵ.2)), which allows us to
deduce after an interpolation the parameters of the calibration line, using the OriginPro-9
software and we get a straight line equation (Ⅵ.1):

y= A +Bx VI.1

With: A = -0.10204

B = 0.37067

Figure Ⅵ.2: Energy calibration line of the gamma spectrometry chain.

Ⅵ.2.2. Efficiency calibration

The measurement of the detector efficiency is obtained experimentally from standard sources:

152
Eu, 241Am and 109Cd, using the relation:

R
¿ VI.2
A∗f

With

ε : detector efficiency (%)

27
 Chapter Ⅵ: Results and discussion

R: the measured activity of the standard source

A: the activity of the standard source on the date of its manufacture

f: the branching factor.

Table Ⅵ.2: Detector efficiency measurements.

Energy (KeV) Efficiency (%) Mistake

59,54 1E-01 1,72E-03
88,03 1,01E-01 1,92E-03
122,06 9,88E-02 1,73E-03
136,55 9,06E-02 2,6E-03
165,86 7,75E-02 4,04E-03
391,7 2,24E-02 3,1E-03
661,66 2,77E-02 5,13E-04
898,04 1,89E-02 2,82E-03
1173,23 1,57E-02 2,73E-04
1332,49 1,41E-02 2,46E-04
1836,05 9,54E-03 5,87E-04

From these results we draw the corresponding graph (figure (Ⅵ.3)), using Origin Pro-9
software in the energy interval [121.87, 1408.08] (KeV).

7.0E-3

6.0E-3

5.0E-3
Efficiency (%)

4.0E-3

3.0E-3

2.0E-3

1.0E-3

250 500 750 1000 1250 1500

Energy (KeV)

Figure Ⅵ.3: Detector efficiency calibration graph.

28
 Chapter Ⅵ: Results and discussion

Ⅵ.2.3. Calibration in Activity

The measured activity is linked to the actual activity of the source by the relationship:

Rmes =A rel × f × Ɛ VI.3

R: the measured activity

f: the branching factor

Ɛ: detector efficiency

60
We calibrated our active samples, using a standard Co calibration source, the following
parameters of which are precisely known:

• Source manufacture date: 01-07-1985

• Activity of the source at the date of manufacture: 460.2 x 103 Bq

Knowing the law of radioactive decay: ( t )= A0 × e− λt , then we deduct the activity from the
d

current source 30-03-2020

Spectral analysis of the standard 60Co source gives the following spectrum (figure (Ⅵ.4)):

Figure Ⅵ.4: Gamma spectrum of the standard source of cobalt.

29
 Chapter Ⅵ: Results and discussion

The analysis of the spectrum obtained gives the following result: For Eγ = 1173.20 KeV, we
find a net area of the peak S net = 27273 (counts) for acquisition time t = 300 s which gives an
activity seen by the detector equal to: Rmeasured = 90.91 (strokes / s). The activity of the source
on 03-30-2020 (the date of the measurement) is A real = 6135 Bq (disintegration / second)

Ⅵ.2.4. Background noise

It is the counting or recording of a spectrum under normal conditions of use of the

measurement chain in the absence of the source whose radiation is to be measured (spectrum

of natural radioactivity from the environment of the chain). It is also defined as the spectrum
recorded from a detector, alone or with an empty container or filled with ultra-pure water.
Knowing this background noise is useful for improving the accuracy of the activity
measurement results, especially in the case of quantitative analysis of trace elements. After
adjusting the γ peaks, we subtract the contribution of the background noise to the peak. We
represent the γ spectrum of the background noise of the γ spectrometry chain (figure (Ⅵ.5)).

2.0E-2

1.5E-2
Cp/s (u.a)

1.0E-2

5.0E-3

0.0
0 250 500 750 1000
Energy (KeV)

Figure Ⅵ.5: γ spectrum of the detector's background noise.

30
 Chapter Ⅵ: Results and discussion

Ⅵ.3. Analysis of experimental results

Ⅵ.3.1. Effect of initial concentration

We represent the effect of the initial concentration of the adsorption of 60Co ions on the
variation of the adsorbed amount of cobalt (60Co) by crude Maghnia bentonite (figure (Ⅵ.6)).

This experiment was carried out under the following conditions:

t = 90 min, pH = 5.5, S / L = 5g / l, T = 313 K

Figure Ⅵ.6: Initial concentration effect of adsorption of 60Co ions.

Thermodynamic equilibrium is reached with a rate in which the constituents of the mixture to
be separated diffuse into the adsorbent and the adsorbent-adsorbate interaction, this
equilibrium is also linked to the initial concentration of the adsorbate. The higher the
concentration, the greater the adsorption capacity, so the process is actually influenced by the
initial concentration.

The increase in the latter causes an increase in the adsorbed quantity of the pollutant. We
notice that the retention rate is important for low concentrations and it continues to increase
until the appearance of a plateau indicating saturation. This can be explained by the
exhaustion of all active sites that exist on the surface of our support.

Ⅵ.3.2. Modeling of adsorption equilibrium isotherms

The study of the equilibrium adsorption isotherm is fundamental to determining the capacity
and nature of adsorption. It is based on the representation by mathematical laws of the

31
 Chapter Ⅵ: Results and discussion

equilibrium relationship between the concentration of the adsorbate at equilibrium (Ce) in

μg / l and the adsorption capacity (qe) in μg / g of the adsorbate by a given adsorbent. There
are many models that have been developed to describe adsorption isotherms such as the
Langmuir and Freundlich models. For the use of these models, we plotted the linear
transformations using the OriginPro-9 software, the parameters of these models as well as the
correlation coefficients (R2) are shown in the table (Ⅵ.4)).

 Langmuir isotherm

The modeling of cobalt adsorption isotherms by raw bentonite by the Langmuir model
(figure (Ⅵ.7)) was performed according to the model given by the Langmuir equation.

Figure Ⅵ.7: Nonlinear Langmuir isotherm.

The quantity adsorbed of metal ion Co2+ on raw Maghnia bentonite increases rapidly for low
concentrations in solution. Then it goes slowly to reach the equilibrium corresponding to a
saturation of adsorption sites. The isotherm obtained is probably of type L according to the
classification of Giles which shows that the process of adsorption of this ion could occur in
monolayers.

The linear form of the Langmuir model is given by the plot of (C e / qe) = f (Ce), with the slope
(1 / qm) and the y-intercept (1 / (qm KL)) this plot allow us to determine the values of the
maximum adsorption capacity necessary for saturation qmax and the Langmuir constant KL.
Figure (Ⅵ.8).

32
 Chapter Ⅵ: Results and discussion

Figure Ⅵ.8: Langmuir isotherm linearized at [T = 313 K].

To validate this model we must calculate the dimensionless Langmuir separation factor

1
R L= VI.4
1+ K L C0

Hence: (RL = 0) irreversible adsorption, (0 <RL <1) favorable, (RL = 1) linear and (RL> 1)
unfavorable

Table Ⅵ.3: Langmuir separation factor according the initial concentration.

C0 RL
0 1
20 5,778E-04
40 2,890E-04
60 1,927E-04
80 1,445E-04
100 1,156E-04
125 9,249E-05
180 6,424E-05
250 4,625E-05
500 2,313E-05

All the values of RL factor range from 0 to 1, where adsorption is favorable.

Increasing the initial concentration results in a decrease in the R L value, indicating that
increasing the initial concentration promotes the process of adsorption of 60Co2 + metal ions
onto the raw bentonite.

33
 Chapter Ⅵ: Results and discussion

We conclude that the retention isotherm of mineral elements is best represented by a

Langmuir isotherm.

 Freundlich isotherm

The modeling of cobalt adsorption isotherms by raw bentonite by the Freundlich model
(figure (Ⅵ.9)) was performed according to the model given by the Freundlich equation which
is used to describe heterogeneous systems.

Figure Ⅵ.9: Nonlinear Freundlich isotherm.

The linear form of the Freundlich model (figure (Ⅵ.10)) is given by the plot of log (q e) = f
(log (Ce)), with the slope (1 / n) and the y-intercept (log (K F)) this plot allow us to determine
the values of the Freundlich constant KF and the intensity of adsorption n.

Figure Ⅵ.10: Freundlich isotherm linearized at [T = 313 K].

34
 Chapter Ⅵ: Results and discussion

Table Ⅵ.4: Langmuir and Freundlich parameters of equilibrium adsorption isotherms of

cobalt on raw bentonite at temperature 313 K.

Langmuir Freundlich

qm (µg/g) 0,0157 1/n 0.259

KL (l/µg) 86,480 KF 0,207

R² 0,97 R² 0,88

According to the results obtained from the adsorption of the metal ion Co 2+ on the crude
bentonite shows that the Freundlich constant n has a value of 3.86 for 313k which means that
the environment is favorable for the adsorption of Co 2+ by crude bentonite because the value
of n must be between 1 and 10 to say that the adsorption is favorable.

The value of the correlation coefficient (R²) of the Langmuir adsorption isotherm is greater
than that of Freundlich. This implies that the Langmuir model better represents the process of
metal ion absorption Co2 + on the raw Maghnia bentonite because its value is closer to 1.

Ⅵ.4. Effect of contact time on adsorption equilibrium

The shape of the experimental points representing the effect of the contact time on the
variation of the adsorbed quantity of cobalt by the raw bentonite (figure (Ⅵ.11)) for
measurement conditions C0 = 100 mg / l, pH = 5.5, S / L = 5g / L, T = 313 K

Figure Ⅵ.11: Effect of contact time on adsorption of 60Co on raw bentonite.

35
 Chapter Ⅵ: Results and discussion

The analysis of the results shows that the cobalt adsorption kinetics take place in two phases,
the 1st phase is rapid in the first 50 minutes of contact for the four temperatures. This is due to
the great availability of the free active sites of bentonite at the start of the adsorption because
the adsorption of Co2+ on the surface constitutes the main part of the process because the
fixation kinetics are limited by the low concentration of cobalt ion remaining in solution, and
the 2nd phase becomes slower and slower during time to reach equilibrium because the
occupation of the adsorption sites requires diffusion within the pores of the adsorbent, thus
limiting the fixation kinetics.

Ⅵ.5. Kinetic modeling of cobalt adsorption on raw bentonite

The modeling of cobalt adsorption kinetics by raw bentonite was performed for four
temperatures (298 K, 313 K, 333 K and 353 K) at a concentration of 100 mg / L using the
pseudo first order and pseudo second order. These models are described in detail in the first
part.

The table below (table (Ⅵ.5)) summarizes the equations used in the line plots of the two
models.

Table Ⅵ.5: Resume of the pseudo first and second order equations.

Model Linear form draw

Pseudo first order Log(qe– qt) = f (t)
log ( q e −q t )=log qe − ( 2.3K ) t
1

Pseudo second order t 1 t t/qt = f(t)

= +
qt K 2 . qe q e
2

36
 Chapter Ⅵ: Results and discussion

Ⅵ.5.1. Pseudo first order model (Lagergren model)

The figures (Ⅵ.12) represent the plots of the pseudo first order kinetic model for the
adsorbent used at C = 100 mg / l for the four temperatures.

The pseudo-first order parameters are summarized in table (Ⅵ.6).

Figure Ⅵ.12: Plots of pseudo first order kinetics at C = 100 mg/l and pH = 5.5.

37
 Chapter Ⅵ: Results and discussion

Ⅵ.5.2. Pseudo second order model

The figures (Ⅵ.13) represent the plots of the pseudo second order kinetic model for the
adsorbent used at C = 100 mg / l for the four temperatures.

The pseudo second order parameters are summarized in table (Ⅵ.6).

Figure Ⅵ.13: Plots of pseudo second order kinetics at C = 100 mg/l and pH = 5.5.

38
 Chapter Ⅵ: Results and discussion

Table Ⅵ.6: Pseudo first / second order results of the adsorption of cobalt 60 on raw bentonite
at C = 100 mg / l.

Pseudo first order

T (K) 298 313 333 353
R2 0.81 0.94 0.929 0.924
qe(cal) (μg/g) .103 6.59 4.03 7.08 10.87
qe(exp) (μg/g) .103 10 12.56 26.3 27.02
K1 0.055 0.011 0.017 0.0109
Pseudo second order
T (K) 298 313 333 353
R2 0.997 0.999 0.999 0.998
qe(cal) (μg/g) .103 10.7 13.1 25.6 28.3
qe(exp) (μg/g) .103 13.6 14.2 28.8 34.9
K2 108.945 105.492 64.5323 19.163

From the graphical results and those of the tables we notice that in the case of first order
kinetics, the best value for the correlation coefficients is 0.94 we can say that is not far from
the unity but the quantity adsorbed at equilibrium determined experimentally is different from
that calculated, which reveal bad model fit.

On the other hand, in the second order model, the quantity adsorbed at equilibrium
determined experimentally is close to that calculated, and the values of the correlation
coefficient are high and very close to unity. It appears that the amount adsorbed at equilibrium
increases while the constant k2 decreases. Which confirms that the pseudo second order is the
most suitable model.

39
 Chapter Ⅵ: Results and discussion

Ⅵ.5.3. Intra-particle diffusion

The representation of this model was by plotting q t = f (t1/2) (figure (Ⅵ.14)) for the adsorbent used
at C = 100 mg / l for the four temperatures.

The parameters of this model are compiled in the table (Ⅵ.7).

T = 298 K T = 313 K

T = 333 K T = 353 K

Figure Ⅵ.14: Plots of the kinetic model of intra-particle diffusion for the temperatures
studied at C0 = 100 mg/l, pH = 5.5.

40
 Chapter Ⅵ: Results and discussion

Table Ⅵ.7: Parameters of the intra-particle diffusion.

intra-particle diffusion
T (K) 298 313 333 353
Kd1 1,5 .10-3 3,72 .10-4 4,59 .10-3 6,73 .10-6

Kd2 1,8 .10-3 2, 19 .10-4 5,88 .10-4 1,31 .10-4

R2 0,98 0,97 0,98 0,97

From the graphical results and those of the tables we notice that the lines of the linear
regression have acceptable correlation coefficients but do not go through the origin, which
means that intra-particle diffusion is involved in the mechanism, but it is not considered to be
the limiting step.

We notice that the diffusion coefficient Kd1 of the first step is high than that of the second step
at T = 313 K and 333 K, therefore we can say that the cobalt ion is firstly adsorbed by the
outer surface with a high speed, and when the process reaches the saturation step the cobalt
ion diffuses into the internal pores within the particles to be adsorbed by the internal surface
of the adsorbent (bentonite).

Ⅵ.6. Study of thermodynamic parameters

The thermodynamic study reflects the spontaneous nature of the adsorption process.
Parameters such as free energy (∆G °), enthalpy variation (∆H °) and entropy variation (∆S °)
can be calculated from parameters determined from equilibrium constants at different
isotherms. The free energy variation of the adsorption reaction is given by:

∆ G=−R T Lnk d VI.5

With

(C e −C 0)
k d= V VI.6
C e∗m

∆ G °=∆ H °−T ∆ S ° VI.7

41
 Chapter Ⅵ: Results and discussion

We plot the function log (Kd) as a function of (1 / T) (K-1), it gives a straight line of slope
(ΔH° / R), and an ordinate at the origin (ΔS° / R). Figure (Ⅵ.15).
The values obtained are presented in the table (Ⅵ.8).

Figure Ⅵ.15: Plot of variation Ln (Kd) as a function of (1 / T).

Table Ⅵ.8: The thermodynamic parameters of adsorption of 60Co ion on the raw bentonite.

T (K) ∆G° (kJ/mol) ∆H° (J/mol) ∆S° (J/mol.K)

298 -13,752
313 -14,446
333 -15,370 17,596 46,21
353 -16,295

According to the results obtained, the adsorption process is endothermic because of the
enthalpy value which is greater than zero (∆H > 0).

The adsorption of cobalt ion on raw bentonite has a physical nature (physisorption) because
the enthalpy value is lower than 40 (KJ / mol), and the negative sign of Gibbs energy
indicates the spontaneity of the adsorption process.

42
Conclusion
 General conclusion

The use of natural clays as an adsorbent for the removal of pollutants from water
contaminated with radioactive ions is a subject of interest, due to their availability in nature,
their low cost and their wide range of applications in various industries. In this study, the raw
bentonite of Maghnia was used for the treatment of the water of the primary circuit of the
nuclear reactor NuR in order to characterize and identify the mechanism of absorption of a
clay medium which is the raw bentonite.

In the first part, our work deals with the operation of the germanium detector Ge (HP) as well
as its calibration in order to be operational in the identification and evaluation of radioactive
elements and their activity.

The adsorption experiments were performed in batch mode, first by varying the initial
concentrations (500, 250, 100, 60, 40, 20) mg / l at the isotherm T = 313 ° K. Then, for the
effect of the contact time at different isotherms (298 K, 313 K, 333 K and 353 K) for the
concentration of 100 mg / l.

Adsorption isotherms were studied at temperature T = 313 K in a typical range of equilibrium

concentration. The adsorption process is endothermic in nature because the elimination of
60
Co is favored by an increase in temperature. Second, it was shown that raw bentonite can
effectively remove 60Co from aqueous solutions.

The spectra of the isotherms at equilibrium were analyzed by the models of Langmuir and
Freundlich where we determined the main parameters of these models as well as the
correlation coefficients R2. In addition, we found that the adsorption equilibrium was
satisfactorily adjusted by the Langmuir isotherm.

In addition, the adsorption kinetics generally follow a pseudo second order law accompanied
by an intra-particle diffusion mechanism, the results indicate that the process is controlled by
intra-particle diffusion and affected by the diffusion film. The thermodynamic study shows
that the adsorption of Co2 + ions on raw bentonite is spontaneous (∆G °<0) and endothermic
(∆H ° = 17.596 J / mol).

As a perspective to this study, we find that raw bentonite is a good candidate for adsorption.
Although the results obtained in the laboratory are satisfactory because we have found that

43
 General conclusion
they agree with those found in the literature, we encourage exploiting these results on a
continuous pilot, with a view to extrapolation to the industrial sector nuclear.

44
Bibliographic
references
[1] N. Bougdah., «Etude de l’adsorption de micropolluants organique sur la bentonite», Thèse

d' Université 20 Août 55, Skikda, pp 30-32, (2007)

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Résumé

Dans cet étude, la rétention des ions radionucléides cobalt-60 présents dans l'eau du circuit
primaire de refroidissement du réacteur NUR a été effectuée dans le but d'évaluer le potentiel
d'adsorption de la bentonite brute de Maghnia. L'étude paramétrique de l'adsorption a été
réalisée à différente températures (298, 313, 33 et 353 K) à pH = 5.5 et S/L = 5 g/l à une
vitesse d'agitation de 450 tr/min, à une concentration égale à 100 mg/l et pour un temps de
contact allant de 1200s. L'étude de la concentration initiale montre qu'elle a influencée sur la
capacité d'adsorption.L'étude des isothermes d'équilibre d'adsorption a montré que le modèle
de Langmuir est le plus approprié pour l'adsorption de cobalt-60 sur la bentonite brute. On a
montré l'effet du temps de contact sur l'adsorption. Les données expérimentales de l'étude
cinétique ont montré que la cinétique d'adsorption de cobalt-60 est de pseudo-second ordre.
Les résultats obtenus ont montré que la diffusion intra-particule est impliquée dans le
mécanisme mais n'est pas considéré comme l'étape limitante, c'est une diffusion dans les
pores. Enfin, l'étude thermodynamique a montré que l'adsorption de cobalt-60 sur la bentonite
brute est de type physisorption et endothermique.

Abstart

In this study, the retention of the cobalt-60 radionuclide ions present in the water of the
primary cooling circuit of the NUR reactor was carried out in order to evaluate the adsorption
potential of raw Maghnia bentonite. the parametric study of the adsorption was carried out at
different temperatures (298, 313, 33 and 353 K) at pH = 5.5 and S / L = 5 g / l at a stirring
speed of 450 rev / min, at a concentration equal to 100 mg / l and for a contact time ranging
from 1200s. The study of the initial concentration shows that it influenced the adsorption
capacity. The study of equilibrium adsorption isotherms has shown that the Langmuir model
is the most suitable for the adsorption of cobalt-60 on raw bentonite. The effect of contact
time on adsorption has been shown. Experimental data from the kinetic study showed that the
adsorption kinetic of cobalt-60 is pseudo-second order. the results obtained have shown that
intra-particle diffusion is involved in the mechanism but is not considered to be the limiting
step, it is diffusion in the pores. Finally, the thermodynamic study showed that the adsorption
of cobalt-60 on raw bentonite is of the physisorption and endothermic type.