SOME ASPECTS OF THE CHEMISTRY
OF
URANYL SELENITES
A THESIS SUBMITTED TO THE
INDIAN INSTITUTE OF TECHNOLOGY, NEW DELHI FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY IN CHEMISTRY
•
V. P. VERMA
DEPARTMENT OF CHEMISTRY FEBRUARY, 1974.
CERTIFICATE
This is to certify that the theSis entitled
" Some Aspects of the Chemistry oftranyl Selenites", being submitted by Mr.V.P.Verma to the Indian: Institute of Technology, Delhi, for the award of the degree of
Doctor of Philosophy in Chemistry, is a record of bonafide research work carried out by him. Mr.V.P.Verma has worked under my guidance and supervision and has fulfilled the
requirements for the submission of this thesis, which to my knowledge, has reached the requisite standard.
The results contained in this thesis have not
been submitted, in part or in full, to any other University or Institute for the award of any degree or diploma.
14 ( B.L.Khandelval) .Thesis Supervisor (R.D.Dua)
Head of Chemistry Department, Indian Institute of Technology, Hauz Khas, New Delhi-110029.
ACKNO WLEDGMENT
It is my profound pleasure and privilege to put on record my deep sense of gratitude to Dr.B.L.Khandelwal,
Assistant Professor of Chemistry Department, Indian Institute of Technology, for his able guidance, unsparing and ever
available help. In fact, but for his help and painstaking supervision and inspiring discussions this work would have never attained this stage.
I take this opportunity to thank Professor R.D.Dual Head of the Department, not only for providing laboratory facilities but also for his allout help whenever and wherever required. Professor Dua helped me in accomplishing this
project by recommending my name for Inteftational Seilahar4 in Chemistry and Chemical Engineering(West Germany) where I could do certain instrumental studies which would have been rather difficult here.
It is indeed a pleasure to acknowledge the help and assistance received from various quarters, especially from Professor E.Fitzer, Dr.W.Weisweiler Karlsruhe University for permitting the use of DTA, Dr.(Miss) G.Weitz Minerology
Department of Karlsruhe University, for help in getting X-ray diffraction patterns, and Miss E.Braendel for preparing X-ray diffraction prints. I am grateful to Dr.B.P.Straughan of
the University of Newcastle Upon Tyne, U.K. for permitting the use of infrared and Raman spectrometers, Mrs.Linda Cook for recording Raman spectra and Mr.B.D.Phloria of Chemistry
Department for recording infrared and visible absorption spectra.
My special thanks are due to Miss K.Raina for reading proofs and manuscript critically.
I acknowledge with thanks for all sorts of assistance and encouragements from my parents, elders, relatives and my wife for her consolations which I required quite often.
Last, surely not the least, my thanks are due to Mr.T.R.Sharma for expert execution of the typing -cork.
1/hrwts;
V.P.VERMA)
To
My eldest Brother without whose help, affection and broad mindedness I could have never completed my academic
education.
CHAPTER.'
CONTENTS
Introduction
1.1 Uranyl Ion and its Tendency
to
form Complexes -
1.2 Aqueous Chemistry of Uranyl ion 1.3 Spectroscopy of Uranyl Compounds 1.4 Uranyl Complexes Containing
M0 11
3 - Ligands.
1.5 Uranyl Complexes with other Ligands
1-27 1
4 5 9 15 Scope of the Present Work 18
References 19
aHAPTER -II Electrometric Studies 28-54
2.1 Introduction 28
2.2 Experimental 38
2.3 Results and DiscussiOn 39
Summary 49
References 51
CHAPTER-III Liquid-Liquid
Distribution
55-80(Solvent
Extraction) and
Spectrophotometric Studies
3.1 Introduction 55
3.2 Experimental 63
3.3 Results
and Discussion
64Summary 76
References 77
CHAPTER-IV Selenito Uranylates 81-124
4.1 Introduction 81
4.2 Techniques used in the Study
of the Compounds 88
4.3 Experimental 96
4.4 Results and Discussion 102
Summary 118
References 119
CHAPTER-V Hydroxo Selenito Uranylates 125-145
5.1 Introduction 125
5.2 Experimental 131
5.3 Results and Discussion 133
Summary 143
References 144
CHAPTER-VI Resume and Scope 146-191
:SS
