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TITLE
CERTIFICATE
PREFACE
ACKNOWLEDGEMENT
CONTENTS
NOTATIONS AND ABBREVIATIONS
LIST OF TABLES
LIST OF FIGURES
I. INTRODUCTION TO THE CHEMISTRY OF THE RARE EARTHS
1.1 Coordination Chemistry of Lanthanides: General
Table 1.1 Comparison of transition metal ions and lanthanide ions
1.2 Coordination Number and Molecular Geometry
Fig. 1.1. Ideal polyhedra for various high coordination numbers.
1.3 Bonding in Lanthanide Complexes
1.4 Applications of Lanthanide Complexes
1.5 Schiff Base Complexes of Yttrium and Lanthanides
II. REAGENTS AND PHYSICOCHEMICAL METHODS
2.1 Reagents
2.1.1 Rare earth oxides
2.1.2 Rare earth salts
2.1.3 Schiff bases
4-N- (4 -Antipyrilmethylidene) aminoantipyrine (AA)
1, 2- (Diimino-4 -antipyrinyl) ethane (GA)
2.1.4 Solvents used
2.1.5 Other reagents
2.2 Analysis of Complexes
2.2.1 Estimation of metal content
2.2.2 Estimation of perchlorate content
2.2.3 Estimation of halide content
2.3 Physicochemical Methods Used in the Present Study
2.3.1 Electrolytic conductance
2.3.2 Magnetic susceptibility
2.3.3 Infrared spectra
2.3.4 Electronic spectral studies
2.3.5 Nuclear magnetic resonance spectral studies
2.3.6 Thermal studies
Thermogravimetry (TG)
Differential Thermal Analysis (DTA)
III. STUDIES ON RARE EARTH COMPLEXES OF 4-N- (4-ANTIPYRYLMETHYLIDENE) AMINOANTIPYRINE EXPERIMENTAL
EXPERIMENTAL
3.1 Procedures for the Preparation of the Complexes
3.1.1 Rare earth perchlorate complexes of AA
3.1.2 Rare earth nitrate complexes of AA
3.1.3 Rare earth chloride complexes of AA
3.1.4 Rare earth bromide complexes of AA
3.1.5 Rare earth iodide complexes of AA
ANALYSIS AND PHYSICOCHEMICAL STUDIES OF THE COMPLEXES
3.2 Results and Discussion
3.2.1 Electrical conductance
3.2.2 Magnetic behaviour
3.2.3 Infrared spectra
Perchlorate complexes
Nitrate complexes
Chloride complexes
Bromide complexes
Iodide complexes
3.2.5 Electronic spectra
Perchlorate complexes
Chloride complexes
Bromide complexes
Iodide complexes
3.2.6 Thermal behaviour
3.3 Summary and Conclusion
Perchlorate complexes
Nitrate complexes
Chloride complexes
Bromide complexes
Iodide complexes
IV. STUDIES ON RARE EARTH COMPLEXES OF 1, 2- (DIIMINO-4-ANTIPYRINYL) ETHANE EXPERIMENTAL
EXPERIMENTAL
4.1 Procedures for the Preparation of the Complexes
4.1.1 Rare earth perchlorate complexes of GA
4.1.2 Rare earth nitrate complexes of GA
4.1.3 Rare earth iodide complexes of GA
ANALYSIS AND PHYSICOCHEMICAL STUDIES OF THE COMPLEXES
4.2 Results and Discussion
4.2.1 Electrical conductance
4.2.2 Magnetic behaviour
4.2.3 Infrared spectra
Perchlorate complexes
Nitrate complexes
Iodide complexes
4.2.4 Proton NMR spectra
4.2.5 Electronic spectra
Perchlorate complexes
Nitrate complexes
Iodide complexes
4.2.6 Thermal behaviour
4.3 Summary and Conclusion
Perchlorate complexes
Nitrate complexes
Iodide complexes
V. STUDIES ON THE KINETICS OF THERMAL DECOMPOSITION OF SOME SELECTED COMPLEXES
5.1 Experimental
5.1.1 Preparation of the ligand and the complexes
5.2 Results and Discussion
5.2.1 Phenomenological aspects
Comparison of the decomposition pattern of the rare earth perchlorate complexes of AA
Comparison of the decomposition pattern of the lanthanum perchlorate, nitrate, chloride, bromide and iodide complexes of AA
Lanthanum perchlorate complex of AA.
Lanthanum nitrate complex of AA
Lanthanum chloride complex of AA
Lanthanum bromide complex of AA
Lanthanum iodide complex of AA
Structure - thermal stability relation
Lanthanum perchlorate complex of GA
Lanthanum nitrate complex of GA
Lanthanum iodide complex of GA
Structure - thermal stability relation
5.2.2 Kinetic aspects
Mechanisrn of reaction
Table V.4. Correlation coefficient calculated using the nine forms of g (α) of rare earth perchlorate complexes of AA
Table V.5. Correlation coefficient calculated using the nine forms of g (α) of lanthanam complexes of AA
Table V.6. Correlation coefficient calculated using the nine forms of g (α) of lanthanum complexes of GA
Rare earth perchlorate complexes of AA
Complexes of lanthanum with AA and GA
Table V.7 Kinetic parameters of the thermal decomposition of rare earth perchlorate complexes of AA
Table V.8 Kinetic parameters of the thermal decomposition of lanthanum complexes of AA
Table V.9 Kinetic parameters of the thermal decomposition of lanthanum complexes of GA
5.3 Summary and Conclusion
VI. SUMMARY
TABLES AND FIGURES
REFERENCES