CHARACTERIZATION OF NICKEL COBALTITE SYNTHESISED

FROM THE PRECURSOR [NiCo2(cit)(N2H4)6](No3)3.

Dissertation

Submitted to Bharathiar University in partial fulfillment of the requirement for the award
of the degree of

MASTER OF SCIENCE IN CHEMISTRY

Done by

JENIFER.E
Reg.No.182CH004

Under the guidance of

Dr. K. KALPANADEVI M.Sc., M.Phil.,Ph.D.,
Associate Professor & Head of the Department

DEPARTMENT OF CHEMISTRY (PG & RESEARCH)

KONGUNADU ARTS AND SCIENCE COLLEGE
[An Autonomous Institution affiliated to Bharathiar University
College of excellence (UGC)]

COIMBATORE – 641 029

March – 2020
DECLARATION
 DECLARATION

I, JENIFER.E, hereby declare the dissertation entitled “CHARACTERIZATION OF

NICKEL COBALTITE SYNTHESISED FROM THE PRECURSOR
[NiCo2(cit)(N2H4)6](No3)3” submitted to Bharathiar University in partial fulfillment of the
requirements for the award of Degree of Master of Science is a record of original project work
done by me under the supervision and guidance of Dr. K. KALPANADEVI M.Sc.,
M.Phil.,Ph.D., Associate Professor Head, Department of Chemistry (PG & Research),
Kongunadu Arts and Science College Coimbatore-641029 and that it has not formed the basis
for the award of any Degree / Associate ship / Fellowship or other similar title to any candidate
of any University.

Date: Signature of the Candidate

(JENIFER.E)
CERTIFICATE
 CERTIFICATE

This is to certify that the dissertation entitled “CHARACTERIZATION OF NICKEL

COBALTITE SYNTHESISED FROM THE PRECURSOR [NiCo2(cit)(N2H4)6](No3)3” has
been carried out by JENIFER.E Reg. No. 182CH004, for partial fulfillment of the
requirements for the award of degree of MASTER OF SCIENCE IN CHEMISTRY, during
the period of (2018-2020) at Kongunadu Arts and Science College, under the guidance of Dr.
K. KALPANADEVI, Associate Professor and Head, Department of Chemistry (PG &
Research), Kongunadu Arts and Science College, Coimbatore-641029 and the dissertation
has not formed the basis for the award of any Degree / Associate ship / Fellowship or other
similar title to any candidate of any University.

Date: Signature of the Guide

Countersigned

Head of the Department Principal

----------------------------------------------------------------------------------------------------------------

1. External Examiner:

2. Internal Examiner:

Date:
ACKNOWLEDGEMENT
 ACKNOWLEDGEMENT

First and foremost, I owe my whole hearted thanks to Almighty for rendering abundant
blessings to carry out my project work.
I thank the Almighty for providing me such a wonderful and enthusiastic guide
Dr. K. KALPANADEVI, MSc., MPhil., Ph.D Assistant professor and Head, Department of
Chemistry (PG & Research), Kongunadu Arts and Science College, Coimbatore, for her care and
encouragement throughout my work. Without her motivation and help it would not have been
possible to bring out this thesis in the present form.
I deeply express my special thanks to:Dr. M. ARUCHAMI, President, Dr. C. A.
VASUKI, Secretary, Dr. M. LEKESHMANASWAMY, Principal, Dr. M. CHINNUSAMY,
Chief Executive Officer (SF), Dr. V. BALASUBRAMANIAM, Dean (Research and
development) and Dr. S. LOGASWAMY, Controller of Examination, Kongunadu Arts and
Science College, Coimbatore, for their encouragement shown towards my carrier.
I render my sincere thanks to the faculty members, Mrs. A. AMUTHAVALLI, Dr. A.
PUSHPAVENI, Mrs. A. NAGAVENI and Mrs. RAMYA Assistant professors, department of
chemistry (PG & Research). Kongunadu Arts and Science College. Coimbatore, for their
valuable suggestions and help.
I thank the non-teaching faculties Ms. VIMALA ANTONY, Department of
Chemistry (PG & Research), Kongunadu Arts and Science College, Coimbatore, for their help
and co- operation throughout my project work.
I acknowledge Kongunadu arts and science college, Coimbatore for providing
instrumentation facility [Shimadzu IR Spectrophotometer(UGC-CE Scheme)]
My ever loving and care taking father and mother, who were the backbone for
each and step of my success throughout my life.
Let me conclude expressing my thanks to all those who have helped me directly or
indirectly to complete this work and whose names do not figure in this lengthy list.

JENIFER.E
CONTENTS
 CONTENTS

CONTENTS

CHAPTER TITLE PAGE NO

I INTRODUCTION 1
II MATERIALS AND
METHODS 10
III RESULT AND
DISCUSSION 17
IV SUMMARY AND
CONCLUSIONS 22

REFERENCES 23
INTRODUCTION
 CHAPTER-I
INTRODUCTION

Coordination chemistry, which is the chemistry of metal complexes, plays a vital role in
industry, technology and life processes. It has always fascinated and inspired chemists all over
the world.

In most coordination compounds, it is possible to identify a central or core atom or ion that
is bonded not simply to one other atom, ion or group through a coordinate bond, but to several of
these entities at once.

The central atom is an acceptor with the surrounding species each bringing atleast one ions
pair of electrons to donate to an empty orbital on the central atom and each of these electron-pair
donars is called a ligand when attached. The central atom is a metal on metalloid, and the
compound that results from bond formation is called a coordination compound, coordination
complex or simply a complex. A coordination complex consists of a central atom, usually a
metal ion, bound to a set of ligands by coordinate bonds.

Coordination chemistry and coordination complexes lie at the core of an array of important
applications in industry, medicine and other fields. Metal-containing coordination compounds
that show a capacity to cure or control a disease have grown remarkably in number and range of
applications in recent decades.

One of the most important human medical applications of coordination compounds is as

chelating agents. Chelating agents are coordination compounds that are either bidentate or
polydentate. A chelating agent used in medicine to capture heavy metals that poison our body,
like lead. EDTA chelates free lead ions, removing then from the blood and tissues and allowing
excretion from the body.[1-5]

Coordination complexes are azed wridely in chemistry as catalysts. Catalysts are chemical
substances that speed up the rate of a chemical reaction. Many enzymes in our bodies require a
metal ion bound in a coordination complex for their actiority. These metal-protein complexes are
called metallo enzymes. Without them, most biological reactions would occur too slowly for life
to exist.

1
 Some examples of coordination complex metallo enzymes are;

• Nickel-complex enzymes as part of the enzymes weak and hydrogenase.

• Cobalt-complex vitamin B12 enzyme cofactor essential to the metabolism of fats,

carbohydrates and proteins.

COORDINATION NUMBER
In chemistry, the coordination number of a central atom in a molecule is the number of
atoms, molecules or ions bonded to it. The ion / molecule / atom surrounding the central
molecule / atom is called a ligand. Coordination number designed originally in 1893 by olfred
Werner is the total number of neighbors of a central atoms in a molecule or ion. The concept is
commonly applied to a coordination complexes.

For molecules and polyatomic ions the coordination number of an atom is determined by
simply counting the other atoms to which is bonded by either single or multiple bonds.

For example, [ Cr ( NH3)2 Cl2 Br2 ]- has Cr3+ as its central cation, which has a coordination
number of 6 and is described as hexacoordinate.

CENTRAL METAL ION

The central metal ion is the metal ion to which the ligands are attached at the center of a
coordination complex. It has a metal ion at its center with a number of other molecule or ions
surrounding it. These can be measured to be attached to the central ion by coordinate bonds.

In the complex ion an acceptor accepts a pair of electrons from the donar atoms. The
acceptor is usually a metal / metal ion to which one or more of neutral molecules or anions are
attached. The acceptor metal cation is referred to as central metal cation. Hence, central metal
cation in a complex serves as a lewis acid.

2
 LIGAND
The neutral molecules or ions which are directly attached to the central metal ion or atom
through coordinate bonds in the complex ion are called ligands. In other words, any species
capable of donating a pair of electrons to a metal is called ligand. A ligand may be an ion,
negatively or positively charged or a neutral molecule.

Ligands should have atleast one lone pair of electrons. It behaves as a lewis base the metal
atom or ion behaves as a lewis acid and an lewis acid-base reaction takes place between them to
form a coordination compound.

Ligands should have the capability to donate their lone pair of electrons to the central metal
atom or ion and form coordinate covalent bond with it.

TYPES OF LIGANDS
Ligands can be classified on the basis of many things. The most common classification of
ligands is on the basis of their binding sites with the central metal atom or ion.

MONODENTATE LIGAND

These are the ligands which coordinate to only one site of a metal ion. In other words, only
one pair of electrons can be donated to the metal ion.

For example, Cl-, Br-, NH3, H2O

BIDENTATE LIGAND

These are the ligands which occupy two sites of a metal ion. i.e, it can be attached to two
metal ion positions.

For example, NH2CH2CH2NH2

POLYDENTATE LIGANDS

These are the ligands which occupy many sites of the same metal ion.

For example, EDTA

This category includes all the higher levels of dentate ligands above bidentate.

For example, tridentate, tetradentate, pentadentate, hexadentate,….etc

3
CHELATING AGENTS

These are the ligands which are bonded with the same central metal atom or ion and form
a ring type structure. Usually bidentate or polydentate ligands fall under this category. Chelating
ligands generally form a ring structure around the central metal atom or ion. The most common
example of these types of ligands is EDTA (ethylene diamine tetra acetic acid)

AMBIDENTATE LIGAND

An ambidentate ligand is that ligand which binds with the central metal atom or ion through
more than one site, usually monodentate ligands fall under this category of ligands. The most
common example of these types of ligand are cyanides (M-CN) and isocyanides (M-NC).

COORDINATION SPHERE
In coordination chemistry, the first coordination sphere refers to the array of molecules and
ions (the ligands) directly attached to the central metal atom. The second coordination
sphere consists of molecules and ions that attached in various ways to the first coordination
sphere.

In crystalline FeSO4.7H2O, the first coordination sphere of Fe2+ consists of six water ligands.
The second coordination sphere consists of a water of crystallization and sulfate, which interact
with the [Fe(H2O)6]2+ centers.[7-15]

4
 CITRIC ACID

Citric acid is a weak organic acid that has the chemical formula C6H8O7. It occurs naturally
in citrus fruits. In biochemistry, it is an intermediate in the citric acid cycle, which occurs in
the metabolism of all aerobic organisms.

More than two million tons of citric acid are manufactured every year. It is used widely as
an acidifier, as a flavoring and a chelating agent.

A citrate is a derivative of citric acid; that is, the salts, esters, and the polyatomic anion found in
solution. An example of the former, a salt is trisodium citrate; an ester is triethyl citrate. When
part of a salt, the formula of the citrate ion is written as C6H5 7O 3-.

Citric acid was first isolated in 1784 by the chemist Carl Wilhelm Scheele, who crystallized it
from lemon juice. It can exist either in an anhydrous (water-free) form or as a monohydrate. The
anhydrous form crystallizes from hot water, while the monohydrate forms when citric acid is
crystallized from cold water. The monohydrate can be converted to the anhydrous form at about
78 °C. Citric acid also dissolves in absolute (anhydrous) ethanol (76 parts of citric acid per 100
parts of ethanol) at 15 °C. It decomposes with loss of carbon dioxide above about 175 °C

USES

• Citric acid is one of the stronger edible acid, the dominant use of citric acid is as a
flavoring and Preservative in food and beverages.
• It is an excellent chelating agent
• Citric acid is used as an acidulant in creams, gels and liquids.
• Its used as an odourless alternative to white vinegar for home dyeing with acid dyes.

5
 HYDRAZINE HYDRATE
Hydrazine hydrate is an inorganic compound with the chemical formula of N2H6O, it is a
colourless, fuming, and oily liquid with an NH3 like odour

Boiling point: 114 °C

Formula: N2H4

Density: 1 g/cm³

Molar mass: 32.0452 g/mol

Melting point: 2 °C

USES

➢ Hydrazine hydrate is used as a reducing agent, an oxygen scavenger in treatment of

boiler water, and as source for drug hydralazine is an anti-tubercular drug.

➢ HH is a reductive agent used as materials of medicine, pesticides, dyes stuff, blowing

agent and photographic developers.

➢ HH has been used as a mineralizers instead of NaOH.

6
 CHEMISTRY OF NICKEL AND ITS COMPLEXES
The element nickel which is a member of group 10 of periodic table. Most compounds in
the group have an oxidation state of +2. Nickel is classified as a tranition metal with nickel (2)
having much chemical behaviour in common with iron (2) and cobalt (2). Nickel forms many
coordination complexes.

Most of the common salt of nickel are green due to the presence of hexaaquanickel(2)ion,
Ni( H2O)6+2. Some nickel compounds are ferromagnetic at sufficiently low temperatures. In
order to show magnetic properties the nickel atoms have to be close enough together in solid
structure.

1.8.1 NICKEL (2) NITRATE

Nickel nitrate is the inorganic compound Ni(NO3)2 or any hydrate thereof.
The anhydrous form is not commonly encountered, thus "nickel nitrate" usually refers to
nickel(II) nitrate hexahydrate. The formula for this species is written in two ways:
Ni(NO3)2.6H2O and, more descriptively [Ni(H2O)6](NO3)2. The latter formula indicates that
the nickel(II) center is surrounded by six water molecules in this hydrated salt. In the
hexahydrate, the nitrate anions are not bonded to nickel. Also known are three other hydrates:
Ni(NO3)2.9H2O, Ni(NO3)2.4H2O, and Ni(NO3)2.2H2O. Anhydrous Ni(NO3)2 is also known.

It is prepared by the reaction of nickel oxide with nitric acid:

NiO + 2 HNO3 + 5 H2O → Ni(NO3)2.6H2O

The anhydrous nickel nitrate is typically not prepared by the heating the hydrates. Rather is
generated by reaction of hydrates with dinitrogen pentoxide or of nickel carbonyl with dinitrogen
tetroxide:

Ni(CO)4 + 2 N2O4 → Ni(NO3)2 + 2 NO + 4 CO

USES

Nickel-containing products play an important role in our daily lives. Compared with other
materials, nickel-containing products possess better corrosion resistance, greater toughness, more
strength at high and low temperatures, and a range of special magnetic and electronic properties.
Therefore, most nickel production is used for alloying elements, coatings, batteries, and some
other uses, such as kitchen wares, mobile phones, medical equipment, transport, buildings, power
generation and jewellery.

7
 CHEMISTRY OF COBALT AND ITS COMPLEXES

In the Periodic Table, close to other transition metals, it is situated in group 8, together
with rhodium and iridium and it can occur in four oxidation states (0, +2, +3 and +4). The +2 and
the ground state are the most common. Cobalt occurs in the minerals cobaltite (Co, Fe) AsS,
smaltite (CoAs2), and erythrite Co3(AsO4)2. 8H2O, and is often associated with nickel, silver,
lead, copper, and iron ores, from which it is most frequently obtained as a by-product.
Depending on the considered species, cobalt has multiple industrial applications including the
production of alloys and hard metal, diamond polishing, drying agents, pigments and catalysts.
Hard metal or cemented carbide is a powder metallurgical product consisting of hard, wear-
resistant carbide particles bound together (cemented) with a ductile metal binder (i. e. metallic
Co) by liquid phase sintering. Tungsten carbide (WC) is produced by mixing tungsten powder
with pure carbon powder at high temperature; hereafter WC is mixed with Co powder to which
paraffin is added as a binder.

1.9.1 COBALT (2) NITRATE

Cobalt Nitrate is the Inorganic compound with the formula Co(NO3)2.xH2O. It
is cobalt(II) salt. The most common form is the hexahydrate Co(NO3)2·6H2O, which is a red-
brown deliquescent salt that is soluble in water and other polar solvent.

USES
Cobalt is used in alloys for aircraft engine parts and in alloys with corrosion/wear
resistant uses. Cobalt is widely used in batteries and in electroplating. Cobalt salts are used to
impart blue and green colors in glass and ceramics.

8
 SCOPE AND OBJECTIVES OF THE WORK

A large number of transition metal complexes have been investigated the last daecades.
There are sample literature on systhesis of cobalt ,nickel bimetallic complex using a variety of
acids as ligand.Since there is no previous study on the synthesis of cobalt,nickel bimetallic
complex using hydrazine hydrate and Citric acid as ligand,it was thought of interest to undertake
such a study. The result of the investigation are described in the

The following are the main objective of the work

• To prepare nickel cobalt Citrate hydrazine nitrate complex using nickel

nitrate, Cobalt nitrate and succinic acid,hydrazine hydrate
• To characterize the ligand and complex by IR spectroscopy
• To analyze the thermal decomposition of prepared complex using TG-
DTA
• To examine the composition of the thermal decomposition product of
prepared Complex (nickel and cobalt oxide)by EDX
• To study the morphology of the nickel and cobalt oxide particles by SEM

9
MATERIALS AND METHODS
 CHAPTER II

MATERIALS AND METHODS

This chapter gives the brief description of the general reagent used in the study.It also
gives the general details of the analytical and physical methods used for the Characterisation of
the complex synthesizied

MATERIALS

Commercially available chemicals (Analar or Equivalent grade) were used as received.

• Citric acid
• Hydrazine hydrate
• Cobalt nitrate
• Nickel nitrate
• Distilled water

SYNTHESIS OF NICKEL COBALT SUCCINATE HYDRAZINIUM NITRATE

COMPLEX

Cobalt nitrate and nickel nitrate taken in 2:1 ratio and mixed with 50ml water. About
1:6 ratio of citric acid and hydrazine hydrate was mixed with 50ml water.Then the two solutions
are mixed together and kept aside without disturbing for few hours. Then the resulting precipitate
are separated and dried.

10
REACTION SCHEME

Ni(NO3)2 + 2Co(NO3)2 + 6N2H6O

C6H8O7

[Ni(Co)2(C6H5O7)(N2H4)6](NO3)3+3HNO3+6H2O

STIOICHIOMETRIC CALCULATION

The required amount of each chemical was weighed using electronic balance
having an accuracy of 10g . The weight percentage of the chemical to be mixed for the sample
was calculated by using the formula

Number of moles= Weight/molecular weight

FOURIER TRANSFORM INFRARED SPECTROSCOPY(FT-IR)

Infrared spectrometry is useful for the identification of both organic and inorganic
compounds. Aggregates of atoms (or functional groups) such as C=O, -NO2, C-N, and C-F; just
to name a few, are all associated with characteristic infrared absorptions. Thus, infrared
spectrometry is ideal for the identification of functional groups present within a sample.

INTERPRETATION OF SPECTRUM

Infrared spectroscopy is the study of the interaction of infrared light with matter. The
fundamental measurement obtained in infrared spectroscopy is an infrared spectrum, which is a
plot of measured infrared intensity versus wavelength (or frequency) of light. In infrared
spectroscopy, units called wavenumbers are normally used to denote different types of light.

11
The IR regions are classified as follows:

Near IR 14,000 - 4,000 cm-1 (wavelength)

(0.8 – 2.5 m) (wavenumber)

Mid IR 4,000 – 400 cm-1

(2.5 – 50 m)

Far IR 400 – 4 cm-1

( 50 – 800 m)

An important observation made by early researchers is that many functional group

absorb infrared radiation at about the same wavenumber, regardless of the structure of the rest of
the molecule. For example, C-H stretching vibrations usually appear between 3200 and 2800 cm-
1
and carbonyl(C=O) stretching vibrations usually appear between 1800 and 1600cm-1. The
region of the infrared spectrum from 1200 to 700 cm-1 is called the fingerprint region. This
region is notable for the large number of infrared bands that are found there. Many different
vibrations, including C-O, C-C and C-N single bond stretches, C-H bending vibrations, and some
bands due to benzene rings are found in this region. The fingerprint region is often the most
complex and confusing region to interpret, and is usually the last section of a spectrum to be
interpreted. However, the utility of the fingerprint region is that the many bands there provide a
fingerprint for a molecule. In fact, the region from 1400-650cm-1 is called finger print region
because the pattern of absorption in this region is unique of a particular compound. The
intermediate portion of the spectrum, especially the 1300-909 cm-1 region, is usually complexes
since both stretching and bending modes gives live to absorption in this region. The absorption
bands in the finger print region are also complexes with the bands originally interacting
vibrational modes. Organic, inorganic and other compounds have their own unique absorption in
this region is particularly rich in absorption bands and shoulders.

12
 Based on intensity, the bands in an infrared spectrum are generally classified. Strong (s),
medium (m), weak (w) and variable (v). The positions of all the bands are expressed in cm-1.

THERMOGRAVIMETRIC ANALYSIS AND DIFFERENTIAL

THERMAL ANALYSIS (TGA/DTA)

Thermogravimetry (TG) is a technique by which the mass of a substrate is measured as a

function of temperature while the substance is subjected to a controlled temperature program.
The record is the TG curve; the mass is normally plotted on the ordinate, decreasing down
towards the origin and temperature(T) or time (t) is one of the abscissa, increasing from left to
right according to the basic rules for plotting any kind of graph. In decomposition reactions, the
mass of reactants disappears and in often replaced by the increasing mass of solid products
formed. Accordingly, in this and subsequent definitions, substance is to be understood to include
the total mass of the system being weighed or investigated.

Differential thermal analysis (DTA) is a technique for identifying and quantitatively

analyzing the chemical composition of substances by observing the thermal behavior of a sample
as it is heated. The technique is based on the fact that as a substance is heated, it undergoes
reactions and phase changes that involve absorption or emission of heat. In DTA the temperature
of the test material is measured relative to that of an adjacent inert material. A thermocouple
embedded in the test piece and another in the inert material are connected so that any differential
temperatures generated during the heating cycle are graphically recorded as a series of peaks on
a moving chart. The amount of heat involved and temperature at which these changes take place
are characteristic of individual elements or compounds; identification of a substance, therefore, is
accomplished by comparing DTA curves obtained from the unknown with those of known
elements or compounds. Moreover, the amount of a substance present in a composite sample will
be related to the area under the peaks in the graph, and this amount can be determined by
comparing the area of a characteristic peak with areas from a series of standard samples analyzed
under identical conditions. The DTA technique is widely used for identifying minerals and
mineral mixtures.

13
 POWDER XRD

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can be provide information on unit cell dimentsions.
The analyzed material is finely ground, homogenized, and average bulk composition is
determined.

FUNDAMENTAL PRINCIPLE OF X-RAY POWDER DIFFRACTION (XRD)

X-ray diffraction is now a common technique for the study of crystal structures and
atomic spacing. X-ray diffraction is based on constructive interference of monochromatic X-rays
and a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample.They are
done using the Brgg’s Law

nλ=2d sin θ

This law relates the wavelength of electromagnetic radiation to the diffraction angle and
the lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed
and counted. By scanning the sample through a range of 2θangles, all possible diffraction
directions of the lattice should be attained due to the random orientation of the powdered
material. Conversion of the diffraction peaks to d-spacings allows identification of the mineral
because each mineral has a set of unique d-spacings.

Typically, this is achieved by comparison of d-spacings with standard reference patterns.

All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are
directed at the sample, and the diffracted rays are collected. A key component of all diffraction is
the angle between the incident and diffracted rays. Powder and single crystal diffraction vary in
instrumentation beyond this.

14
 SEM (SCANNING ELECTRON MICROSCOPY)

The scanning electron microscope (SEM) uses a focused beam of high-energy

electrons to generate a variety of signals at the surface of solid specimens. The signals that derive
from electron-sample interactions reveal information about the sample including external
morphology (texture), chemical composition, and crystalline structure and orientation of
materials making up the sample. In most applications, data are collected over a selected area of
the surface of the sample, and a 2-dimensional image is generated that displays spatial variations
in these properties. Areas ranging from approximately 1 cm to 5 microns in width can be imaged
in a scanning mode using conventional SEM techniques (magnification ranging from 20X to
approximately 30,000X, spatial resolution of 50 to 100 nm).

Fundamental Principles of Scanning Electron Microscopy (SEM)

These signals include secondary electrons (that produce SEM images), backscattered
electrons (BSE), diffracted backscattered electrons (EBSD that are used to determine crystal
structures and orientations of minerals), photons (characteristic X-rays that are used for
elemental analysis and continuum X-rays), visible light (cathodoluminescence--CL), and heat.
Secondary electrons and backscattered electrons are commonly used for imaging samples:
secondary electrons are most valuable for showing morphology and topography on samples and
backscattered electrons are most valuable for illustrating contrasts in composition in multiphase
samples (i.e. for rapid phase discrimination). X-ray generation is produced by inelastic collisions
of the incident electrons with electrons in discrete ortitals (shells) of atoms in the sample. SEM
analysis is considered to be "non-destructive"; that is, x-rays generated by electron interactions
do not lead to volume loss of the sample, so it is possible to analyze the same materials
repeatedly.

EDX (ENERGY DISPERSIVE X-RAY) SPECTROSCOPY

Energy dispersive x-ray is a standard method for identifying and quantifying elemental
compositions in a very small sample of material (even a few cubic micrometers).

15
 In a properly equipped SEM, the atoms on the surface are excited by the electron beam,
emitting specific wavelengths of X-rays that are characteristic of the atomic structure of the
elements. An energy dispersive detector (a solid-state device that discriminates among X-ray
energies) can analyze these X-ray emissions. Appropriate elements are assigned, yielding the
composition of the atoms on the specimen surface. This procedure is called energy dispersive X-
ray spectroscopy.

Energy-dispersive X-ray spectroscopy (EDX) is used to analyze the elemental

composition of solid surfaces. X-ray emission is stimulated by the irradiation of the surface with
a high energy beam of charged particles or a focused X-ray beam. Excitation of the electronic
structure of an atom can produce an X-ray emission, the energy signature of which is a unique
characteristic of each element. Therefore a “fingerprint” or “signature” spectrum can be obtained
allowing element identification via comparison with reference spectra.

Furthermore, EDX can be used for qualitative (the type of elements) as well as
quantitative (the percentage of the concentration of each element of the sample) analysis. In most
SEMs, dedicated software enables auto-identification of the peaks and calculations of the atomic
percentage of each element that is detected. One more advantage of the EDX technique is that it
is a non-destructive characterization technique, which requires little or no sample preparation.

16
RESULTS AND DISCUSSION
 CHAPTER III
RESULTS AND DISCUSSION

IR Spectral Analysis
From the IR spectrum of [NiCo2(C6H6O7)(N2H4)6](NO3)3, the N–N stretching frequency
can be identified at 972 cm-1, which unambiguously proves the bidentate bridging nature of the
hydrazine ligand. The asymmetric and symmetric stretching frequencies of the carboxylate ions
are seen at 1549 and 1240 cm-1, respectively with the ∆γ(asymm-sym) separation of 309 cm-1, which
indicates the monodentate linkage of the carboxylate groups. The N–H stretching is observed at
3162 cm-1. A very strong band at 1389 cm-1 and a medium band at 846 cm-1 are attributable to γ3
and γ2 vibrations of uncoordinated nitrate ions of D3h symmetry [R1]. The IR data thus confirms
the formation of the above mentioned complex.

Table 3.2 IR spectral data

Assignment Wavenumber cm-1
γ - (asymmetric) 1549
coo

γ - (symmetric) 1240
coo

γ 972
N-N

γ 3162
N-H

γ 1389 (s)
NO3
846 (m)

17
 Fig.3.1 IR spectrum of the complex

Thermal analysis
From the TG-DTA pattern of the complex, the following observations are made. The
complex loses the uncoordinated NO3 species in the temperature range of 90℃ 𝑡𝑜 180℃, the
corresponding DTA curve for such a change is noticed as a small exotherm. In the temperature
range 370℃ 𝑡𝑜 430℃, all the citrate and hydrazine moieties are lost, leaving behind Nickel
cobaltite NiCo2O4.

COMPLEX DTA PEAK ℃ TG TEMP ℃ DECOMPOSITION PRODUCT

110 90 - 180 Ni(Co)2(C6H5O7)(N2H4)6

[Ni(Co)2(C6H5O7)(N2H4)6](NO3)3
400 370 - 430 NiCo2O4
[Ni(Co)2(C6H5O7)(N2H4)6](NO3)3

18
 1.800
25.00 3.000

1.600
20.00 2.500

1.400
15.00 2.000

1.200 1.500
10.00
DTA uV

TG mg
1.000 1.000
5.00

0.800 0.500
0.00

0.000
0.600
-5.00

-0.500
0.400
-10.00
-1.000
0.200
-15.00
-1.500
0.000
100.0 200.0 300.0 400.0 500.0
Temp Cel

EDX ANALYSIS
EDX spectrum of the sample is presented in Fig. 3.3, which provides its actual chemical
composition. There are no unwanted peaks in the EDX spectrum, confirming the purity of the
sample. The metal oxide particles are expected to be in the nanoscale.

4000 O

3000
INTENSITY (a.u)

2000
Co
O
1000 Co Ni
Co Ni
Ni

0 5 10 15 20
ENERGY (Kev)

Fig.3.3 EDX Spectrum

19
 XRD ANALYSIS
The XRD pattern of NiCo2O4 nano particle is shown in Fig 3.4. In the diffractional study
2𝜃 values confirms the presence of NiCo2O4 nano particle. The sharp peaks are indicated (311),
(400), (331), (442) and (533) in Fig.3.4 matches well with JCPDS card no.(73-1704) of NiCo2O4
and this facts also confirms the presence of NiCo2O4. The average crystalline size of NiCo2O4
was calculated using debye scherrer equation was found to be around 15 nm.

Fig.3.4 XRD pattern

SEM ANALYSIS
The morphology of the sample is understood from its SEM images, shown in Fig. 3.5.
From the images, it is clear that the sample possesses typical and definite spheres.

20
Fig 3.5 SEM images of NiCo2O4 nano particles

21
CONCLUSION
 CHAPTER-IV
SUMMARY AND CONCLUSIONS
The present work contains the preparation and characterization of
[Ni(Co)2(C6H5O7)(N2H4)6](NO3)3 complex. IR spectrum of the complex has been found to
justify the structural features of [Ni(Co)2(C6H5O7)(N2H4)6](NO3)3 complex. From the IR
spectral data it is confirmed that the ligand coordinate with the metal ion through the carbonyl
oxygen of the carboxylic acid group. The TG-DTA pattern of the complex showed a two step
process, yielding NiCo2O4 as the final product. SEM images contain typical and definite spheres.
EDX analysis confirms the purity of the sample.

22
REFERENCES
REFERENCES
1. G.J.Durant,G.M.Smith,R.G.W.Spicket,S.H.B.Wright,J.Med. chem..,9,(1966),22-27.

2. R. McGill, U. S. Patent 2, 033, 203 (1936); Chem. Soc., 109, Abst., 30,2992.

3. David J. Aitken, Alberto Albinati, Arnaud Gautier, Henri-Philippe, Husson, Eur. J. Inorg.
Chem.., (2007), 3327-3334.

4. E.B. Miminoshvili, A.E.Shvelashvili, T.O.Vardosanidze, Zh.Neorg.Khim., 41, No12, 2066-

2068 (1996).

5. G.V.Romanenko, Z.A.Savelyeva, N.V.Podberezskaya, et al., Zh.Strukt.Khim. 35, No 3, 48-

55,(1994).

6. Philip J. Bailey, Keith J. Grand, Stuart Pace, Simon Parsons and LisaJ.Stewart Chem.Soc.,
Dalton Trans., 1997, p 4263-4266.

7. A.E. Shvelashvili, E.B. Miminoshvili, V.K.Belsky, and T.O.Vardosanidze, ibid., No.9, 1345-
1347.

8. E.V.Miminoshvili, V.K.Belsky, T.N.Sakvarelidze.J.Struct.Chem.Vol.46, No.6, pp. 1086-

1090 (2005).

9. I.V. Medrish, A.V. Vologzhanina, Z.A. Starikova, M.Yu. Antipin, Russian. J. Inorg. Chem;
50, (2005), 360-364.

10. William T.A. Harrison, Mark L.F. Phillips, Tina M. Nenoff, International.J. Inorg. Mat., 3,
(2001), 1033-1038.

11. S. Maia, J.R.; Gazard, P.A.; Kilner, M. Batsanova, A.S.; Howard,J.A.K.J.Chem.Soc., Dalton
Trans. 1997, 4625

12. Ma K.T. Tin, Glenn P.A. Yap, and Darrin S.Richeson. Inorg.Chem. 37, 6728-6730 (1998).

23
13. J.Thiele, Ann., 273,(1893), 133

14. G.H.Jeffery, J. Bassett, J. Mendham and R.C.Denney, “Vogel’s Textbook of Quantitative

Chemical analysis” 5th Ed., (1986).

15. Heyn, French patent; 618, 064, chem.zent. 1927, 503.

16. Kikukawa N., Takemori M., Nagano Y., Sugasawa M. and Kobayashi S., Synthesis and
magnetic properties of nanostructured spinel ferrites using a glycine–nitrate process, J. Magn.
Magn. Mater., 284, 206 (2004)

17. Prakash A.S., Khadar A.M.A., Patil K.C. and Hegde M.S., Hexamethylenetetramine: A New
Fuel for Solution Combustion Synthesis of Complex Metal Oxides, J. Mater. Synth. Process., 10,
2002 (2002)

18. Vaidyanathan G., Sendhilnathan S. and Arulmurugan R., Structural and magnetic properties
of Co1−xZnxFe2O4 nanoparticles by co-precipitation method, J. Magn. Magn. Mater., 313, 293
(2007)

19. Azadmanjiri J., Salehani H.K., Barati M.R. and Farzan F., Preparation and electromagnetic
properties of Ni1−xCuxFe2O4 nanoparticle ferrites by sol–gel autocombustion method, Mater.
Lett., 61, 84 (2007)

20. Ahmed M.A. and El-Sayed M.M., J. Magn. Magn. Mater., Magnetic characterization and
thermoelectric power of Ni1−yZny Cu0.3Fe1.7 O4, 308, 40 (2007)

21. Kim C.K., Lee L.H., Katoh S., Murakami R. and Yoshimura M., Synthesis of Co-, Co-Zn
and Ni-Zn ferrite powders by the microwave-hydrothermal method, Mater. Res. Bull., 36, 2241
(2001)

22. Moumen N. and Pileni M.P., New Syntheses of Cobalt Ferrite Particles in the Range 2−5
nm: Comparison of the Magnetic Properties of the Nanosized Particles in Dispersed Fluid or in
Powder Form, Chem. Mater., 8, 1128 (1996)

24
23. Song Q. and Zhang Z.J., Correlation between Spin−Orbital Coupling and the
Superparamagnetic Properties in Magnetite and Cobalt Ferrite Spinel Nanocrystals, J. Phys.
Chem., B110, 11205 (2006)

25. Han M., Vestal C.R. and Zhang Z.J., Quantum Couplings and Magnetic Properties of
CoCrxFe2-xO4 (0 < x < 1) Spinel Ferrite Nanoparticles Synthesized with Reverse Micelle
Method, J. Phys. Chem., B108, 583 (2004)

26. Mahmoud Goodarz Naseri , Elias B. Saion, Hossein Abasstabar Ahangar, Abdul Halim
Shaari, Fabrication, characterization, and magnetic properties of copper ferrite nanoparticles
prepared by a simple, thermal-treatment method, Materials Research Bulletin 48 (2013) 1439–
1446

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