SYNTHESIS AND CHARACTERIZATION OF BENZOIC HYDRAZIDE COMPLEX OF

LEAD (II) NITRATE

BY

LUQMAN MOHAMMED YAHAYA

(SCI15CHM042)

A DISSERTATION
SUBMITTED TO THE
DEPARTMENT OF CHEMISTRY
FACULTY OF SCIENCE
FEDERAL UNIVERSITY LOKOJA

IN PARTIAL FULFILLMENT OF
THE REQUIREMENT FOR THE
DEGREE OF

BACHELOR OF SCIENCE (B.Sc.) (Hons.) IN

CHEMISTRY

NOVEMBER, 2019

i
 Declaration

I hereby declare that this project titled “Synthesis and Characterization of Benzoic Hydrazide

Complex of Lead (II) Nitrate” was carried out by me in the Department of Chemistry Federal

University Lokoja, Kogi State, Nigeria, under the supervision of Dr. O.W Salawu. The information

derived from the literature has been duly acknowledged in the text and a list of references provided.

No part of this project has been presented for another degree or diploma at any institution.

Luqman Mohammed Yahaya Date

SCI15CHM042

ii
 Certification

This is to certify that this work was carried out by LUQMAN MOHAMMED YAHAYA in

partial fulfillment of the award of B.sc (Hons.) Degree in Chemistry, Department of Chemistry,

Federal University Lokoja

Dr. O.W Salawu Date

(Project Supervisor)

Dr. Isah Yinusa Date

(Head of Department)

Prof. S.O Okeniyi Date

(External Examiner)

iii
 Dedication

This project is dedicated to almighty Allah for giving me wisdom, sound health, favour and life.

To Him alone belong all the glory and adoration.

iv
 Acknowledgement

Glory be to almighty Allah the lord of the world, the most magnificent, the most merciful. I

sincerely thank my able supervisor Dr. O.W Salawu for his wisdom, knowledge and wise counsel

throughout my work, who is willing to go through my work and effect corrections, making sure

he pushed me to bring out the best in me. Special thanks to all the lecturers and staff of the

department of chemistry Federal University Lokoja who are numerous for me to mention, for their

contribution directly or indirectly to the progress of this work. My sincere gratitude goes to Mr.

Mohammed Adamu Danlami also Mr. Edward Adegbe and Mr. Mohammed Audu of chemistry

laboratory.

I thank my parents profoundly for their love; endless support and timely advice, which have

shielded and cushioned me from major obstacles and challenges throughout my life. My deepest

gratitude to all family members for their prayers, encouragement and most especially my loving

brother and Sisters, for their care and love.

v
 TABLE OF CONTENT

Title page …….……………………………………………………………………………………i

Declaration ………………………………………………………………………………………..ii
Certification …………………………………………………………………………..………….iii
Dedication ………………………………………………………………………………......……iv
Acknowledgement ………………………………………………………………………………..v
Tale of content …………………………………………………………………………………………………………………..…....vi-viii

List of Figure ………………………………………………………………………………..….ix

List of table ………………………………………………………………………………………x

Appendix………………………………………………………………………………………….xi

Abstract ………………………………………………………………………………………….xii

CHAPTER ONE ............................................................................................................................. 1

1.0 BACKGROUND OF STUDY .................................................................................................................... 1

1.1 STATEMENT OF PROBLEM .................................................................................................................. 1

1.2 AIMS AND OBJECTIVES OF THE STUDY ............................................................................................... 3

1.3 SIGNIFICANCE OF THE STUDY ............................................................................................................. 3

1.4 SCOPE OF THE STUDY.......................................................................................................................... 3

1.5 HYDRAZIDE .......................................................................................................................................... 4

1.6 METAL COMPLEXES............................................................................................................................. 5

1.7 TRANSITION METAL ............................................................................................................................ 6

1.7.1 Application ....................................................................................................................................... 6

CHAPTER TWO ............................................................................................................................ 8

2.0 LITERATURE REVIEW ........................................................................................................................... 8
vi
 2.1 INSTRUMENTAL APPLICATIONS ........................................................................................................ 11

2.1.1 UV-Vis Spectroscopy ...................................................................................................................... 11

2.1.2 Magnetic Susceptibility Measurement .......................................................................................... 12

2.1.3 Infrared Spectroscopy (IR) ............................................................................................................. 13

2.1.4 Principle of Infrared Spectroscopy ................................................................................................. 14

CHAPTER THREE ...................................................................................................................... 16

3.0 MATERIALS AND METHODS .............................................................................................................. 16

3.1. Reagents, Solvents and Instruments................................................................................................ 16

3.1.2 Instruments/Apparatus.................................................................................................................. 16

3.1.3 Preparation of the ligand ............................................................................................................... 17

3.1.4 Preparation of Benzoic acid hydrazide (Ligand) ............................................................................ 17

3.1.5 Preparation of the complexes........................................................................................................ 17

3.1.6 Preparation of Pb[BH] Complex ..................................................................................................... 17

3.1.7 Melting point/decomposition of the Ligand and the Complex ..................................................... 18

3.2.0 Magnetic Moment Determination ................................................................................................. 18

3.2.1 Solubility Determination for Ligand and the Complexes ............................................................... 18

3.2.4 Spectroscopic Study of the Hydrazide and the Complex ............................................................... 18

3.2.5 Infrared Spectra ............................................................................................................................. 18

3.2.6 Electronic Spectra Studies.............................................................................................................. 19

CHAPTER FOUR ......................................................................................................................... 20

4.0 Results, Discussion, Conclusion and Recommendation. ................................................................... 20

4.1 Result and Discussion........................................................................................................................ 20

vii
 4.1.1 Hydrazide ....................................................................................................................................... 20

4.1.2 The formation of Complexes.......................................................................................................... 20

4.1.3 Magnetic Susceptibility .................................................................................................................. 21

Magnetic moment measurement was used to determine the presence of paired and unpaired d-
electron in a transition metal complex. The result is shown below. ...................................................... 21

4.1.4 Solubility test for the Ligand and Complexes ................................................................................ 21

4.1.5 Infrared Spectra Data ..................................................................................................................... 22

4.1.7 Infrared Spectra of Lead Complex ................................................................................................. 23

4.1.8 UV- visible Spectra Data ................................................................................................................. 24

4.1.9 Conclusion ...................................................................................................................................... 25

4.2.0 Recommendation........................................................................................................................... 26

REFERENCE ................................................................................................................................ 27

viii
 LIST OF FIGURE

Figure 1: p-Toluenesulfonylhydrazide and 2,4,6-triisopropylbenzenesulfonylhydrazide …… 1

Figure 2: Heterocyclic Compound Hydrazide ……….……………………………………….. 1

Figure 3: General Preparation of Hydrazide from Ester……………………………………….14

Figure: 4 Diagrammatic Instrumentation of Ultraviolet Spectrophotometer ………………….17

Figure:5 Diagrammatic Instrumentation of Infrared Spectroscopy…………………………….19

Figure: 6 Synthesis of Benzoic acid hydrazide (Ligand)……………………………………….21

Figure: 7 Complexation of Benzoic acid hydrazide ……………………………………………21

ix
 LIST OF TABLE

Table 1: Magnetic Susceptibility Test Results of the Ligand and Complex…………………25

Table 2: Solubility Test Results of the Ligand and Complex………………………………..26

Table 3: Important features of the IR from the complexes ………..………………………...27

Table 4: UV.VIS Electronic spectra data……………………….……………………………29

x
 LIST OF APPENDICES

Appendix 1a: IR result for the hydrazide…………………………………………………………29

Appendix 1b: IR result for the complex…………………………………………………………..29

Appendix 2a: Uv result for the complex …………………………………………………………30

xi
 ABSTRACT

The ligand benzoic hydrazide (BH) and its complexes with Pb(II) nitrates were successfully

synthesized and characterized by magnetic susceptibility, melting point, electronic and infrared

studies. Infrared data suggest that the ligand is neutral bidentate donors ligating through the

carbonyl oxygen and the azomethine nitrogen towards the metal ions. The nitrate ion is in the

outer coordination sphere in the complexes. The magnetic and electronic spectral data indicate

tetrahedral structures geometry has been suggested for the metal complex.

xii
 CHAPTER ONE

1.0 BACKGROUND OF STUDY

The coordination chemistry of transition metals with ligands from the hydrazide family has been

of interest due to different bonding modes shown by these ligands with both electrons rich and

electron poor metals. Hydrazides play an important role in inorganic chemistry as they easily form

stable complexes with most transition metal ions. The development of the field of bioinorganic

chemistry has increased the interest in Hydrazide complexes, since it has been recognized that

many of these complexes may serve as models for biologically important species. Hydrazides have

often been used as chelating ligands in the field of coordination chemistry and their metal

complexes are of great interest for many years. The remarkable biological activity of acid

hydrazides R–CO–NH–NH2, and the dependence of their mode of chelation with transition metal

ions present in the living system have been of significant interest. Hydrazide metal complexes have

been widely studied because they have industrial, antifungal, antibacterial, anticancer and

herbicidal applications, it was report the synthesis and structural studies of the ligands and

complexes isolated from the reactions of acetic acid (4-methyl-benzylidene) hydrazide (L1) and

acetic acid (naphthalen-1-ylmethylene) hydrazide (L2) with copper (II) nitrate. (Saber et al., 2010).

1.1 STATEMENT OF PROBLEM

It is estimated that 3.3 billion people were at risk of malaria in 2011 and, 80% of malaria cases and

90% deaths caused by malaria occur in Africa, with children under the age of five and pregnant

women being the most severely affected (World Health Organization, 2012). The eradication of

1
malaria and other diseases such as tuberculosis (TB) continues to be frustrated by drug resistance

development of the disease-causing organisms. Drug resistivity of the malaria parasite P.

falciparum to chloroquine has been reported for decades (Daniel, 2009; Kiremire, 2010; WHO,

2014), however, cases of parasite resistance to the drug currently used, Artemisinin, have been

reported in some parts of the world (WHO, 2014). In events of the cases spreading to more parts

of the world, public health will be under risk as there is no alternative antimalarial medicine

available for at least the next five (5) years (WHO, 2014). This highlights a great need for a

continued search for more compounds which are cheaper and more effective against these disease-

causing organisms. The hydrazide properties are of major interest due to their biological activities.

Hydrazides have been demonstrated to possess, amongst others, antibacterial, antifungal, and

antitumoral activities. These properties are sometimes enhanced on coordination to certain

transition metal ions. The formation of metallic complexes plays an important role in the

enhancement of their biological activity and therefore, many complexes of hydrazides have been

synthesized and characterized. Some of these metal complexes also exhibit better fungicide,

antitumoral and antibacterial activities. Recent studies have shown several new compounds of

isonicotinic acid hydrazide being synthesized to evaluate the effects of carbonyl compounds on

the biological activity of isonicotinic acid hydrazide and the effect of metals like Zn (II), Ni (II),

Co (II) and Cu (II) on the antibacterial activity of these compounds. In this study, the synthesis,

characterization and antibacterial activities of metal complexes derived from isonicotinic acid

hydrazide were reported. (Olalekan et al., 2018).

2
 1.2 AIMS AND OBJECTIVES OF THE STUDY

The aim of this research study is to synthesize, characterize ligand (Benzoic acid hydrazide) and

its metal complex (Lead nitrate).

The specific objectives are as follows.

 To prepare the ligand (Benzoic acid hydrazide).

 To complex the ligand (Benzoic acid hydrazide) with Pb(NO3)2 salts in solution.

 To characterise the complex by Infrared, UV-visible spectrophotometer, magnetic susceptibility

and to study the possible geometry and the coordination of these metal ions to the ligand.

 To determine the possible structure for the complex compound.

1.3 SIGNIFICANCE OF THE STUDY

Hydrazides constitute an important class of biologically active organic compounds and their

therapeutic uses are well documented. Hydrazides and their condensation products are reported to

possess a wide range of biological activities including antibacterial activity, tuberculostatic

properties, HIV inhibitors, pesticidal, antifungal and many more. Some of the hydrazides and

corresponding hydrazones are psychopharmacological agent, eg, monoamine oxidase (MAO)

inhibitor and serotonin antagonists. This research will aid development of new biological,

pharmaceutical and chemotherapeutical information for future references.

1.4 SCOPE OF THE STUDY

This research work covers the synthesis, characterization of Lead II (Pb2+) complexes derived from

benzoic acid hydrazide using Infrared, UV-visible spectrophotometer, magnetic susceptibility and
3
its metal complexes and also proposing possible structure for the complex, possible geometric and

coordination of the metal ions to the ligand.

1.5 HYDRAZIDE

Hydrazides are a class of organic compounds sharing a common functional group characterized

by hydrazine core in which at least one of the hydrogen atoms is replaced by a substituent that is

an acyl group. The general structure for a hydrazide is E(=O)-NR-NR2, where the R's are

frequently hydrogen. Hydrazides can be further classified by atom attached to the oxygen:

carbohydrazides (R-C(=O)-NH-NH2), sulfonohydrazides (R-S(=O)2-NH-NH2) and phosphonic

dihydrazides (R-P(=O) (-NHNH2). The related hydrazines do not carry an acyl group. Some

important members of this class are sulfonylhydrazides such as ptoluenesulfonylhydrazide which

are useful reagents in organic chemistry such as in the Shapiro reaction and the Eschenmoser–

Tanabe fragmentation. This reagent can be prepared by reaction of tosyl chloride with hydrazine.

(IUPAC, 2016).

Figure: 1 p-Toluenesulfonylhydrazide and 2,4,6-triisopropylbenzenesulfonylhydrazide

4
Hydrazides have also been used as important intermediates in synthesis of various heterocyclic

compound such as 1,2,4-triazoles, 1,3,4-thiadiazoles, 1,3,4 oxadiazoles, 1,2,4,5-tetrazines, which

are known to possess diverse pharmacological properties. (Ashish, et al., 2012).

Figure: 2 Heterocyclic Compound Hydrazide

/

1.6 METAL COMPLEXES

Lead(II) nitrate is an inorganic compound with the chemical formula Pb(NO3)2. It commonly

occurs as a colourless crystal or white powder and, unlike most other lead(II) salts, is soluble in

water. nitrate from either metallic lead or lead oxide in nitric acid was small scale, for direct use

in making other lead compounds. In the 19th century lead(II) nitrate began to be produced

commercially in Europe and the United States. Historically, the main use was as a raw material in

the production of pigments for lead paints, but such paints have been superseded by less toxic

paints based on titanium dioxide. Other industrial uses include heat stabilization in nylon and

polyesters, and in coatings of photothermographic paper. Since around the year 2000, lead(II)

nitrate has begun to be used in gold cyanidation. (Haynes, 2011).

5
1.7 TRANSITION METAL

The term transition element, as defined by IUPAC, is the element with a partly filled d orbitals in

its ground state or in any of its oxidation state. This definition justifies the inclusion of Cu, Ag and

Au as transition metals, since Cu(II) has a 3d9 configuration, Ag(II) has a 4d9 and Au(III) has a

5d8 configuration. By this definition, Zn, Cd and Hg are excluded from transition metals, as they

have d10 configuration. However, being the end members of the series, they are often considered

together with the transition elements. (Khandelwal, 2012).

Transition metals are all metals of economic importance. They are found in the d-block of the

periodic table between group 2 and group 3. They occupy three rows, with ten elements in each

row. Most of the transition metal complexes are colored and their colors are different from the

transition metal salts and the ligands, then this is an important indication to the occurrence of

coordination (Nwabueze and Salawu, 2012).

1.7.1 Application

Current applications of lead (II) nitrate include use as a heat stabilization in nylon and polyesters,

in thermographic printing paper, and in rodenticides. To improve the leaching process in the gold

cyanidation process, lead (II) nitrate solution is added. Although a bulk process, only limited

amounts (10 to 100 milligrams lead (II) nitrate per kilogram gold) are required. Both the

cyanidation itself, as well as the use of lead compounds in the process, are deemed controversial

due to the compounds' toxic nature. On a laboratory scale, lead (II) nitrate may be used to make

nitrogen dioxide. The dry compound is heated in a steel vessel, producing nitrogen dioxide gas,
6
which dimerizes to dinitrogen tetroxide when condensed to a liquid or when it is dissolved in an

organic solvent. Pb(NO3)2 → PbO2 + 2NO2 in organic chemistry, lead (II) nitrate has been used as

an oxidant, for example as an alternative to the Sommelet reaction for oxidation of benzylic halides

to aldehydes. It has also found use in the preparation of isothiocyanates from dithiocarbamates.

Because of its toxicity it has largely fallen out of favour, but it still finds occasional use, for

example as a bromide scavenger during SN1 substitution. (Haynes et al., 2011).

7
 CHAPTER TWO

2.0 LITERATURE REVIEW

Complexes of isonicotinic acid hydrazide with Cu,2+ Co2+ and Ni2+ have been prepared and

characterized by analytical and physiochemical techniques, such as elemental analysis, melting

point determination and solubility studies, magnetic susceptibility and conductivity measurements,

electronic and IR spectral studies. The infrared spectral studies revealed the bidentate nature of the

Hydrazide in the complexes; the ligand acting as neutral bidentate donor coordinating to the metal

through the carbonyl O and the azomethine N. An octahedral geometry is suggested for all the

complexes. (Ama et al., (2017).

Nwabueze and Salawu, (2012), stated that metal complexes formed by the reactions of keto and

enol forms of isobutryl acetic acid hydrazide [IBAH], 4- amino benzoic acid hydrazide[4-ABAH]

and 4-cyano benzoic acid hydrazide [4-CBAH] with Ni2+ and Cu2+sulphate ions were prepared and

characterized by elemental analysis, IR, and electronic absorption spectra studies. The results

showed that the Hydrazides reacted with the metal salts in 1:2 molar ratios in all the complexes

and acts as neutral bidentate ligands. The solubility test on the ligands and its metal complexes

revealed their solubility in ethanol and dimethylsulphoxide (DMSO).

Sarala et al., (2015), stated that copper complex of type [Cu(SBH)2] in which salicylaldehyde

benzoyl hydrazide (SBH) was synthesized and characterized by different analytical procedure and

spectral studies. The complex was insoluble in common organic solvents and it has melting point

in between 254-258oC. Infrared spectrum showed the bonding through enolic oxygen and

8
azomethine nitrogen. The electronic spectral studies showed that the Cu2+ is in tetrahedral

coordination environment. The hydrazides based on R-CONHNH2 and their derivatives contain

trigonal N- and O- donors making them potential chelating ligands. Hydrazide derivatives and

complexes have supra molecular interactions because they include the hydrogen-bonding donors

(amino group) and acceptors (carbonyl), and as a result hydrogen – bonding plays an important

role in extending and stabilizing the structures of the resultant complexes. The mode of

coordination of benzoic hydrazide to Li+, Zn2+, Cd2+, Hg2+ and Mg2+ were reported. The

luminescence properties of Zn (II) and Cd (II) complexes of N’-(2-hydroxybenzoyl)

isonicotinohydrazide and N’ (2hydroxybenzoyl) nicotinohydrazide had been investigated. Also,

the mode of coordination and the biological activity of some Zn(II) complexes with acetic acid (3-

chloro-4-hydroxyl benzylidene)-hydrazide and acetic acid(2-nitro-benzaylidene) hydrazide have

been found out to have interesting biological applications, Hence, the interest in the syntheses,

physicochemical properties, mode of coordination and the stability of some metal (II) complexes

of isovaleric acid hydrazide. (Aliyu HD, 2013).

A variety of methods have been used to prepare hydrazides, by reaction of acids or their derivatives

with hydrazine hydrate, acid chlorides and acyl anhydrides were used to prepare hydrazides. The

reaction of acid chlorides and acyl anhydrides with hydrazine often leads to the formation of diacyl

derivatives due to their high reactivity. Hydrazides are commonly prepared by the hydrazinolysis

of esters with hydrazine hydrate. Esters being less reactive are not converted into diacyl derivatives

but require longer periods for conversion to hydrazides which vary from hours to several days.

9
The use of inclusion complexes of hydroquinone and hydrazine in solid state hydrazinolysis of

esters and MW irradiation technique has also been reported. Much attention is given to

acylhydrazides and some other hydrazine derivatives because of their biological and physiological

activities. They generally exhibit very strong anti-microbial activity. This activity is enhanced on

complexation to some metal ion. They are also used to produce high polymer substances and in

the determination of metal by complexation (Nwabueze, 2012).

Generally, the acylhydrazides are found to be potentially tridentate ligands. Their metal complexes

especially copper (II) have been known to show anti-tumor activity while some others are used in

polymer coating and pigments. The remarkable biological activity of acid hydrazides R-CO-NH-

NH2 and the dependence of their mode of chelating with transition metal ions present in living

system have been of significant interest in the past. The co-ordination compounds of acylhydrazide

have been reported to act as enzymes inhibitors and are useful due to their pharmacological

application. (Adekunle et., al 2013).

Adekunle et al., (2012), carried out analysis on Cu complexes of benzoic acid hydrazide (BAH)

and P- substituted methyl benzoic acid hydrazide (MBAH). The magnetic susceptibility, electronic

and infrared spectral data were consistent with amononuclear square planar geometry with

bidentate coordination of the hydrazide ligands to give essentially a CuN2 chromophore.

According to Aishish et al., (2012), chelate of benzoic acid hydrazide (BAH) with nickel (II) and

manganese (II) nitrate was prepared. The complex and ligand were characterized by Fourier

transform infrared spectra analysis, electronic spectra analyses, conductivity, melting point, and

10
solubility. The FTIR analysis indicated that the ligand (BAH) coordinated through carbonyl

oxygen and the primary amine nitrogen. This is an indication that the ligands acted as tridentate

and bidentate donors to the metal ions. The electronic spectra showed the complexes of Ni BAH

as octahedral geometry.

2.1 INSTRUMENTAL APPLICATIONS

2.1.1 UV-Vis Spectroscopy

UV-Vis Spectroscopy is an analytical method used to measure the absorbance of ultra-violet or

visible radiation through an analyte. The molecular absorption of the analyte corresponds to both

excitation of valence electrons and excitation of electrons in different atomic orbitals.

UV-Vis Spectroscopy is an effective technique for both qualitative and quantitative analysis of

organic and inorganic compounds. UV-Vis Spectroscopy is based on the Lambert-Beer principle

which states that the Absorbance of a solution (A) is directly proportional to its pathlength (l) and

its concentration (c) when the wavelength of the incidence light remains fixed. This is summarized

as A = ε/c where ε is the molar absorptivity. (Fanidul et al., 2015).

The UV-visible Spectrophotometer is the analytical instrument used for the UV-visible

spectroscopic analysis. Spectrophotometers are available in different configurations however most

can be categorized into either single beam, split beam or double beam types depending on the

design of their optical system. Such types of instrument comprise the following components in

their constructions: (Paula et al., 2009).

 Light Source

11
  Monochromator

 Cell Compartment

 Detector

 Signal Processing System.

Figure 4: Diagrammatic Instrumentation of Ultraviolet Spectrophotometer

2.1.2 Magnetic Susceptibility Measurement

Magnetic moment measurement can be used to determine the presence of paired and unpaired

d-electron in a transition metal complex. Basically when the transition metals ion or their

complexes are placed in a magnetic field, they show different behavior, on the basis of their

behavior, these substances have been classified as para-magnetic substances and diamagnetic

substances. The transition metal complexes whose central metal ion contains one or more

12
 unpaired electron are paramagnetic while those, whose central atom has no unpaired electron

i.e all their electrons are paired, behave as di-magnetic substance. The effective magnetic

moment can be obtained from experimentally determined molar magnetic susceptibility which

is expressed in βM or µeff.

µeff = 2.828 Xm x T

Where T is the room temperature = 298k.

However, in transition metal complexes, the orbital contribution is largely “quenched” by the field

due to the surrounding ligands. Therefore, the “spin-only” formula is given as

μeff = √[n(n+2)] BM

Where n is the number of unpaired electrons in the metal ion.

2.1.3 Infrared Spectroscopy (IR)

Infrared spectroscopy is a very powerful technique which uses electromagnetic radiation in the

infrared region for the determination and identification of molecular structure as well having

various quantitative applications within chemistry. The IR spectroscopy concept can generally be

analyzed in three ways: by measuring reflection, emission, and absorption. The major use of

infrared spectroscopy is to determine the functional groups of molecules. (Peter, 2011).

The energy required to excite the bonds belonging to a molecule, and to make them vibrate with

more amplitude, occurs in the infrared region. A bond will only interact with the electromagnetic

13
infrared radiation, however, if it is polar. The presence of separate areas of partial positive and

negative charge in a molecule allows the electric field component of the electromagnetic wave to

excite the vibrational energy of the molecule. The change in the vibrational energy leads to another

corresponding change in the dipole moment of the given molecule. The intensity of the absorption

depends on the polarity of the bond. Symmetrical non-polar bonds in N≡N and O=O do not absorb

radiation, as they cannot interact with an electric field. Regions of the Infrared Spectrum Most of

the bands that indicate what functional group is present are found in the region from 4000 cm to

1300 cm. Their bands can be identified and used to determine the functional group of an unknown

compound. Bands that are unique to each molecule, similar to a fingerprint, are found in the

fingerprint region, from 1300cm to 400cm. These bands are only used to compare the spectra of

one compound to another. (Brian, 2011).

2.1.4 Principle of Infrared Spectroscopy

The IR spectroscopy theory utilizes the concept that molecules tend to absorb specific frequencies

of light that are characteristic of the corresponding structure of the molecules. The energies are

reliant on the shape of the molecular surfaces, the associated vibronic coupling, and the mass

corresponding to the atoms. For instance, the molecule can absorb the energy contained in the

incident light and the result is a faster rotation or a more pronounced vibration. (Carlo et al., 2010).

14
Figure 5: Diagrammatic Instrumentation of Infrared Spectroscopy

15
 CHAPTER THREE

3.0 MATERIALS AND METHODS

3.1. Reagents, Solvents and Instruments.

Methyl benzoate and hydrazine hydrate was purchased from BDH chemical company limited and

used without further purification. The salts: Pb(II) nitrate, Silica gel, ethanol and hydrazine hydrate

were obtained in chemistry laboratory Federal University Lokoja, Kogi State. The IR spectra were

recorded on an IR spectrophotometer Cary 630 using KBr technique at chemistry laboratory,

Kwara State University Ilorin, Nigeria. The UV-visible spectra were recorded on a UV- visible

spectrophotometer Beckman DU640 in absolute ethanol solution reagents and solvents used were

purchased from BDH chemical company limited, they were of analytical grade therefore used

without further purification. The magnetic susceptibility was determined with the aid of Mk1

Magnetic Susceptibility Balance at Chemistry Department laboratory of Kwara State University

Ilorin, Nigeria.

3.1.2 Instruments/Apparatus

 Magnetic stirrer

 Refluxing apparatus (Galen champ heating mantle)

 Desiccator

 Analytical weighing balance

 Filter paper

 Beaker
16
  Conical flask

 UV – visible spectrophotometer

 IR spectrophotometer

 Round bottom flask

3.1.3 Preparation of the ligand

3.1.4 Preparation of Benzoic acid hydrazide (Ligand)

The benzoic acid hydrazide, C6H5CONHNH2, (BH), was prepared by the condensation of ester

with hydrazine hydrate.30ml (0.3mol) of methyl benzoate was added to 60ml (0.6mol) of

hydrazine hydrate in 60ml (0.6mol) of absolute ethanol. The mixture was refluxed for 6-8 hours

in a round bottom flask, after which it was poured into a beaker. The solution was left for two (2)

days to crystallise, the crystals obtained was filtered, dried over silica gel in a desiccator for about

two (2) days and weighed after which it was stored in a sample bottle. (Salawu et al., 2011).

3.1.5 Preparation of the complexes

3.1.6 Preparation of Pb[BH] Complex

2g (0.008mol) of benzoic acid hydrazide [BAH] was dissolved in 30ml(0.03mol) of ethanol and

2g (0.008mol) of (PbNO3).5H2O was dissolved in 30ml of distilled water (H2O) and the [BH] was

then poured gently into the lead (II) solution on the magnetic stirrer with constant stirring for about

15 minutes. It was left for about an hour to cool. They were filtered and dried over silica gel in the

desiccator for about two (2) days, the crystals were weighed and kept in a sample bottle. (Salawu

et al., 2011).
17
3.1.7 Melting point/decomposition of the Ligand and the Complex

The melting point/decomposition apparatus was used in the determination of the melting point

decomposition temperature of the complexes and the ligand were taken in an open capillary tube.

3.2.0 Magnetic Moment Determination

This was carried out with the aid of Mk1 Magnetic Susceptibility Balance at Chemistry

Department laboratory of Kwara State University Ilorin, Nigeria. The result is shown in table 1 in

chapter four.

3.2.1 Solubility Determination for Ligand and the Complexes

The solubility of the ligand and the metal complexes were studied in various solvents such as

petroleum ether, methanol, ethanol, chloroform, benzene and distilled water was carried out by

shaking a small amount of the ligand and the complex in a test tube and the result is given in Table

2 in chapter four.

3.2.4 Spectroscopic Study of the Hydrazide and the Complex

3.2.5 Infrared Spectra

This was carried out with the aid of IR spectrophotometer Cary 630 using KBr at Chemistry

Department laboratory of Kwara State University Ilorin, Nigeria. The result is recorded in table 3

in chapter four.

18
3.2.6 Electronic Spectra Studies

This was carried out using UV-vis spectrophotometer Beckman DU640 at Chemistry Department

laboratory of Kwara State University Ilorin, Nigeria. the result is recorded in table 4 in chapter

four.

19
 CHAPTER FOUR

4.0 Results, Discussion, Conclusion and Recommendation.

4.1 Result and Discussion

4.1.1 Hydrazide

The preparation of the hydrazide as a ligand from methyl benzoate and hydrazine hydrate is

represented in the equation below. Complex are obtained upon the reaction of Pb (II) nitrate with

the ligand. The complex is colourless, solid and soluble in organic solvents such as ethanol and

methanol. The benzoic acid hydrazide was obtained in a good yield. The complexes and the ligand

are quite stable in air. They could be stored for months without any appreciable change

(Nwanbueze and Salawu, 2012). The magnetic susceptibility measurement indicates that the

complex is diamagnetic.

C6H5COOCH3 + N2H4.H2O 60ml ethanol C6H5CON2H3 + CH3OH + H2O

Reflux-8hrs

Figure 6: Preparation of Benzoic acid hydrazide

4.1.2 The formation of Complexes

The formation of the complexes from the ligand and the metal ions is represented by the equation

shown below.

C6H5CON2H3 + Pb(NO3)2.5H2O Heat [Pb (BH)2]NO3.2H2O + 3H2O

Figure 7: Preparation of the Complexes

20
 4.1.3 Magnetic Susceptibility

Magnetic moment measurement was used to determine the presence of paired and unpaired d-

electron in a transition metal complex. The result is shown below.

Table 1: Magnetic Susceptibility Test Results of the Ligand and Complex

Compound Emperical Formula Formula Colour Melting % yield Magnetic

Weight point susceptibility

(oC)

[BAH] C6H5CON2H3 136.154 White 114 95%

464.7 Colourless 470 54% -74.0 x 10-6

[Pb(BAH)2]NO3.2H2O [Pb(C6H5CON2H3)2]

NO3.2H2O

4.1.4 Solubility test for the Ligand and Complexes

The solubility test for the ligand and the complexes were carried out using different solvents and

the result is shown in the Table 4. It shows that the ligand and the complexes are soluble in ethanol

and methanol. This may be due to the polymeric nature of the complex (Salawu and Abdulsalam,

2011). The ligand and metal complexes show similar solubility behavior in all the solvents. They

are generally soluble in polar organic solvents and the result can be seen in the table below:

21
Table 2: Solubility Test Results of the Ligand and Complex

Compound Ethanol Methanol Distilled Petroleum Benzene Chloroform

H2O ether

Ligand Soluble Soluble Insoluble Insoluble Insoluble Soluble

(BAH)

[Pb2+BH] Soluble Soluble Insoluble Insoluble Insoluble Insoluble

4.1.5 Infrared Spectra Data

The present ligand and the metal complexes were analyzed by IR spectroscopy. The salient

features of IR spectra of compounds are summarized in (Table 3). The IR spectra of the complexes

are compared with that of the ligand to determine the changes that might have taken place during

the complexation (Kehinde et at., 2015). There is a general displacement due to the coordination

process found in the result. In appendix, infrared spectra of the ligand and the complexes are given.

There are three major vibrations that have been used successfully to make coordination of ligands

to the metal in the spectra of complexes of hydrazide (Krishna et al., 2010). These are the υ(C=O),

the carbonyl stretching mode called “amide I” band, the coupling between the in plane bending

υ(N-H) and υ(C-N) called the “amide II” band and the stretching frequency for the amino group

υ(NH2) (Salawu et al., 2011).

In the hydrazide, the amino group band υ(NH2) was observed at a medium strong band centered

at 1663cm-1. This band was shifted to a lower wave number in the complex around 1640 cm-1 for

22
Pb2+ and 1655 cm-1. This indicates the coordination of the metal ion to the amino group (Salawu

et al., 2011).

4.1.7 Infrared Spectra of Lead Complex

As stated earlier, the absorption frequencies are found in Table 6 as well as the absorption

frequencies of Pb complex, the region 899 cm-1 and 810 cm-1 were assigned to υ(NH) bend mode

respectively. In the corresponding ligand these frequencies for same group were observed at

672cm-1. An upward shift of the bands was observed by the complexes which indicates that the

υ(NH) group of the ligand is coordinated to metal ion via its azomethine nitrogen.

The medium to strong band in the region 1607cm-1 in the IR spectra of Pb complex were assigned

to carbonyl υ(C=O) stretching vibration. These bands in the corresponding ligand appeared in the

range of 1618 cm-1. The change in the distribution of electrons and molecular environment around

the ligand is due to introduction of metal ions caused by minor shift in the position. This also

indicates that the hydrazide also coordinates through the carbonyl oxygen (Ushma and Sunil,

2014). The stretching vibrations of the nitrate ion are usually observed at the range of 1350-

1450cm-1 (Monfared et al., 2011). Since nitrate ions of the complexes are assigned to the range of

1354cm-1 and 1361cm-1 respectively, then it can be said that the nitrate ion maybe found at the

outer coordination sphere in the complexes, since it falls within the range at which the nitrate

absorbs.

23
 Table 3: Important features of the IR from the complexes

S/N Peak Bond Groups Frequency Range

values (cm-1)
(cm-1)
1 3299.94 N-H Stretching Amide 3100-3500 cm-1
2 2876.55 C-H stretching Alkanes 2850-2970 cm-1
3 1487.95 C-N Stretching Amide 1350-1500 cm-1
4 1618. υ(C=O) Amide I band 1630-1680cm-1
5 1616.93 NH2 Amide II band 1630-1680cm-1
6 884.84 υ(NH) NH bend mode 690-900 cm-1
7 1567.03 C=C Aromatic 1475-1600 cm-1
8 684.87 Mono- Aromatic 680-910
substituted
benzene
9 1354 NO3 Nitrate 1350-1450cm-1

4.1.8 UV- visible Spectra Data

UV-visible Spectroscopy is an analytical method used to measure the absorbance of ultra-violet or

visible radiation through an analyte. The molecular absorption of the analyte corresponds to both

excitation of valence electrons and excitation of electrons in different atomic orbitals. The

electronic absorption spectra of metal complexes were recorded in the range of 799.9nm for the

complexes and at room temperature. Electronic spectra of the complex are shown in appendix and

the spectra data are given in Table 4.

The Pb2+ ion with d10−configuration in a complex can be either be tetrahedral or square planar

geometry (Nwabueze and Salawu, 2012).

24
Table 4: UV.VIS Electronic spectra data

S/N Compound ʎmax(nm) Assignment Geometry

(BAH) 347 -
n → σ*
1 n → π*
π → π*.

2 [Pb(BAH)2]NO3.nH2O 796 - Tetrahedral

4.1.9 Conclusion

The newly synthesized hydrazide and its complexes were subjected to spectral studies such as IR,

Uv and magnetic susceptibility measurement as well as anti-bacterial screening. The melting point

determination carried out shows that the melting point is sharp which indicates the purity of the

prepared compounds. The IR spectra of the hydrazide containing a strong C=O absorption band at

1618cm-1and N-H absorption band at 672cm-1and NH2 absorption band at1663cm-1 after

complexation, these bands were shifted to a lower and higher wave number indicating the

involvement of the oxygen atom in chelate formation respectively. The magnetic measurement

result showed that the complexes is diamagnetic.

25
4.2.0 Recommendation

Other complexes derived from benzoic acid hydrazide should be synthesized and characterized by

more sophisticated technique such as XRF analysis, mass spectroscopy, H1-NMR, elemental

analysis and X-ray crystallography. Analysis such as Magnetic Susceptibility, Conductivity

Measurement should be carried out as well to confirm the correct structures for the complexes as

proposed. Effect of the complexes on all bacteria and fungi species should be carried out.

Hydrazide should be synthesized from aromatic ester as it gives more yield compared to aliphatic

ester.

26
 REFERENCE

Adekunle F.A.O, Woods J A O, Odunola O A. (2013). Zinc (II) Complexes of Symmetrical bis-
hydrazide ligands: Synthesis, Characterization and Properties. Res J Pharm Biol Chem Sci;
4(1): 401- 403.

Adekunle, F.A, Woods, J.A. Onawunmi, O.E. and Odunola, O.A. (2012). Synthesis,
Characterization and Structural Studies of Cu2+ Complexes of Benzoic Acid Hydrazide.
Synthesis and Reactivity in Inorganic, Metal-Organic and Nano Metal Chemistry Journal,
Vol. 46(7), 340-387.

Aliyu HD, Ojo AS. (2013). Complexes of Cu (II) and Ni (II) Sulphate with Acetone and
Acetaldehyde Hydrazones Derived from Valeric Acid and Isovaleric Acid. Asian J Chem;
24(3): 961-963.

Ama, S.O. Salawu, O.W. and Onu, A.D. (2017). Synthesis, Characterization and Antimicrobial
Activities of Isonicotinic Acid Hydrazide and its Complexes. Few Trends in Science and
Technology Journal, 244-246.

Ashish, K., Anshu, J. and Makrandi J.K. (2012). A Highly Efficient Solvent Free Synthesis of
Hydrazides Using Grinding Technique.

Brian C.S. (2011). “Fundamentals of Fourier Transform Infrared Spectroscopy” Chapters 1 to 3.

CRC Press. United States of America.

Carlo L, Adriano Z., Elena G. and Silvia B. (2010). “Probing the Surfaces of Heterogeneous
Catalysts by in situ IR Spectroscopy” Chem. Soc. Rev. 394951-5001.

27
Daniel, L. S. (2009). The Synthesis and characterization of copper (II) complexes containing
thiosemicarbazone and semicarbazone ligands derived from Ferrocene and pyridyl
fragments. Chem.Soc.Rev.38765.

Fanidul, I. Amiran, M.H. Nur, M. and Hridika, T. (2015). Synthesis, Characterization and Anti-
microbial Activities of Ni(II) Complexes with Pyridine as the Ligand. Journal of Inorganic
Chemistry, Vol. 1(2).

Gamil, A.A. and Nashwa, E. (2017). A Series of Nickel Complexes Derived from Hydrazide
Derivatives, Electrochemical, Thermal and Spectral Studies. Arabian Journal of Chemistry,
10, S1003–S1013.

Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca
Raton, FL: CRC Press. p. 4.70. ISBN 1439855110.

Hogan, C.M. (2010). "Heavy metal" in Encyclopedia of Earth. National Council for Science and
the Environment. E. Monosson and C. Cleveland (eds.) Washington DC.

IUPAC, (2016). Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") Online
corrected version: "Hydrazides ". doi:10.1351/goldbook.H02879.

Khandelwal, B.L. (2012). Chemistry of Transition Elements. Pearson Education Delhi. P: 438-
431.

Kiremire, E. (2010). Method of synthesizing a complex active against the malaria parasite
plasmodium falciparum. US Patent App. 13/642,615.

Meija, Juris; et al. (2016). "Atomic weights of the elements 2013 (IUPAC Technical Report)".
Pure and Applied Chemistry. 88 (3): 265–91. doi:10.1515/pac-2015-0305.

28
Mohamed, D. Samuel, A.A. and Sunil, I. (2016). Synthesis, Characterization and Antimicrobial
Activity of Some Novel Hydrazide 3d Transition Metal Complexes derived from
dihydropyrimidinone and 4-aminoanti-pyrine, J. Chem. Sci., 4, 11–17.s

Muddassar, S. Ammar, B.S. Sohail, A. and Naveed, A.D. (2013). Synthesis and Biological
Evaluation of Hydrazide Based sulfonamides benzoic acid Hydrazides. Advances in Pure
and Applied Chemistry.Vol. 1. No.2 pp.40-48.

Nwabueze, J.N. and Salawu, O.W. (2012). Complexes of Co (II) and Mn (II) Sulphates with Keto
and Enol forms of Isobutryl acetic acid, 4- Amino benzoic acid and 4-Cyano. Journal of
Scientific and Innovative Research, vol. 2 (3): 627-633.
Olalekan, W.S., David, A.O and Kenneth, I.N. (2018). Synthesis, Characterization and
Antibacterial Activity of Isonicotinic Acid Hydrazide Complexes with Co (II), Cu (II), Mn
(II) and Zn (II) ions. Nigerian Research Journal of Chemical Sciences, Vol. 5, 2018.

Paula, P. Atkins, A. and Julio, D. (2009). Elements of Physical Chemistry. Oxford: Oxford. Pp
459

Peter J.L (2011). “Infrared and Raman Spectroscopy. Principles and Spectral Interpretation”
Chapters 1 to 6. Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands. Elsevier.

Saber, R., Shahriare, G., Kheyrollah, M., And Hajar, S. (2010). Synthesis, Characterization and
Thermal Analysis of new Cu (II) Complexes with Hydrazide Ligands.e-journals175-p23-56.

Sarala, D.C. Nagula, N. Palreddy, R. Jaheer, M. and Boinala, A. (2015). Synthesis

Characterization and Biological Studies of Novel (16z)-1-ethyl-1, 4-dihy-dro-n'-(1-3, 4-
dihydro-6-methyl-2,4-dioxo-2h-pyran-3-yl ethylidene)-7-methyl-4-oxo-1,8-naphthyridine 3
carbohydrazide) and its Cu (II), Ni (II) and Co (II) Complexes International Journal of
Research in Pharmacy and Chemistry; 5(4), 615-633

29
Scerri, E. R. (2011). A Very Short Introduction to the Periodic Table. Oxford: Oxford University
Press.

WHO (2012). Antimicrobial activity of different thiosemicarbazone compounds against microbial

pathogens. International Research Journal of Pharmacy, 3(5), 350–363.

WHO. (2014). “Malaria threat and public health”. Journal of Microbiology.Vol:6.3456475699.

30
 APPENDICES

Appendix 1a: IR result for the hydrazide

Appendix 1b: IR result for Lead complex

31
Appendix 2a: Uv result for Pb complex

0.700

0.280
7

0.000
200.00 360.00 600.00
nm.

32