METHODS OF COMPLEX ANALYSIS

SD9900046

PREPARATION OF PHENACYLCHLORIDE,
MORPHOLINOPHENACYL AND N-PIPERIDINOPHENACYL
OXIMES AND STUDY OF THEIR COMPLEXATION
WITH COPPERdD AND COBALT(II) IONS




A THESIS SUBMITTED
FOR THE DEGREE OF M.SC.




BY:-
KAMAL ELDIN AHMED ALI
B.SC. (HONOURS)



DEPARTMENT OF CHEMISTRY
FACULTY OF SCIENCE
UNIVERSITY OF KHARTOUM




30-47

, DISCLAIMER


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illegible in electronic image products.
Images are produced from the best
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, TABLE OF CONTENTS
Acknowledgement IV
Dedication V
Abstract IV
CHAPTER ONE
1. Introduction 1
1.1 General Remarks 1
1.2 d-Block elements 1
1.3 General properties of d-block elements 1
1.4 Co-ordination chemistry of copper(II) complexes 2
1.5 Co-ordination chemistry of cobalt(II) complexes 3
1.6 Ligands 4
1.6.1 Classification of ligands 5
1.6.2 Chelate system 5
1.6.3 Factors which affect chelate formation 5
1.6.4 Oxime ligands 6
1.6.6 Oxime chelate complexes 6
1.7 Solvent extraction of metals 7
1.7.1 Choice of solvent for extraction 8
1.7.2 Stripping 8
1.7.3 Types of solvent extraction 9
1.7.4 Quantitative aspect of solvent extraction 9
1.7.5 Advantages of solvent extraction 10
1.8 Physicochemical methods for determination of
stoichiometry and stability constant 10
1.8.1 Colligative properties 10
1.8.2 Colourimetry and spectrophotometry 11
1.8.2.1 a-Continuous variation method 11
1.8.2.2 b-Mole ratio method 11
1.8.2.3 c-Slope ratio method 12
1.9 Method of determination of copper 12
1.10 Method of determination of cobalt 13
CHAPTER TWO
2. Experimental 14
2.1 Preparation of oxime ligands 14
2.1.1 Preparation of phenacyl chloride 14
2.1.2 Preparation of phenacyl chloride oxime 14
2.1.3 Preparation of morpholino-phenacyl oxime 15
2.1.4 Preparation of N-piperidino-phenacyl oxime 15
2.2 Reagents grade 16
2.2.1 pH-determining solutions 16
2.2.2 Acetate buffer solutions 16
2.2.3 Oxime solutions 16
2.2.4 Salt solutions 16
2.2.5 Organic solvent 17
2.2.6 Instruments 17
2.3 Study of oxime metal Ion complexes 17
2.3.1 Identifications of specific wavelength of
maximum absorbances 17
2.3.2 Effect of pH 17

, 2.3.3 Effect of time 18
2.3.4 Stoichiometry of metal ion-oxime complexes 18
2.3.4.1 Mole-ratio method 18
2.3.4.2 The continuous variation method 18
2.3.4.3 Determination of the formation constant 19
2.3.4.4 Slope ratio method 20
2.3.5 Effect of solvent 20
2.4 Determination of copper as diethyldithiocarbamate complex 21
2.5 Quantitative colourimetric determination of cobalt using
2-Nitrosonaphthol reagent 21
2.6 Study of copper(II) morpholinophenacyl oxime complex 22
2.7 Study of copper(II) N-piperidinophenacyl oxime complex 32
2.8 Study of phenacylchloride oxime copper(II) complex 43
2.9 Determination of copper (II) as diethyldithiocarbamate 53
2.9.1 Determination of extraction percent of morpholinophenacyl
oxime ligand 55
2.9.2 Determination of extraction percent of Copper (II) with
N -piperidinophenacyl oxime ligand 55
2.9.3 Determination of extraction percent of Copper (II) with
phenacylchloride oxime ligand 55
2.10 Study of morpholinophenacyl cobalt(II) oxime complex 56
2.11 Study of N-piperidinophenacyl cobalt(II) oxime complex 65
2.12 Quantitative colourimetric determination of cobalt using
2-Nitroso-l-naphthol reagent 76
2.12.1 Determination of percentage extraction of cobalt(II)
with phenacyl oxime ligands 78
2.12.2 Preparation of copper(II) and cobalt(II) complexes
in solid form 78
2.12.3 Physicochemical analysis of phenacyl oxime ligands 78
2.12.4 Physicochemical analysis of phenacyl oxime complexes 79
CHAPTER THREE
3. Discussion 80
4. References 83